Nothing Special   »   [go: up one dir, main page]

WO2014203100A2 - Alkali-ion conductive separator assembly for rechargeable electrochemical cells - Google Patents

Alkali-ion conductive separator assembly for rechargeable electrochemical cells Download PDF

Info

Publication number
WO2014203100A2
WO2014203100A2 PCT/IB2014/061752 IB2014061752W WO2014203100A2 WO 2014203100 A2 WO2014203100 A2 WO 2014203100A2 IB 2014061752 W IB2014061752 W IB 2014061752W WO 2014203100 A2 WO2014203100 A2 WO 2014203100A2
Authority
WO
WIPO (PCT)
Prior art keywords
alkali
ion conducting
separator assembly
range
porous membrane
Prior art date
Application number
PCT/IB2014/061752
Other languages
French (fr)
Other versions
WO2014203100A3 (en
Inventor
Heino Sommer
Jochen REINACHER
Jürgen Janek
Stefan BERENDTS
Original Assignee
Basf Se
Justus-Liebig-Universität Giessen
Basf (China) Company Limited
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Basf Se, Justus-Liebig-Universität Giessen, Basf (China) Company Limited filed Critical Basf Se
Priority to CN201480034089.1A priority Critical patent/CN105409051A/en
Priority to US14/899,899 priority patent/US20160141580A1/en
Priority to JP2016520768A priority patent/JP2016526757A/en
Priority to EP14814477.7A priority patent/EP3011629A4/en
Priority to KR1020167001310A priority patent/KR20160021841A/en
Publication of WO2014203100A2 publication Critical patent/WO2014203100A2/en
Publication of WO2014203100A3 publication Critical patent/WO2014203100A3/en

Links

Classifications

    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/054—Accumulators with insertion or intercalation of metals other than lithium, e.g. with magnesium or aluminium
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M12/00—Hybrid cells; Manufacture thereof
    • H01M12/08—Hybrid cells; Manufacture thereof composed of a half-cell of a fuel-cell type and a half-cell of the secondary-cell type
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
    • H01M50/403—Manufacturing processes of separators, membranes or diaphragms
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
    • H01M50/409—Separators, membranes or diaphragms characterised by the material
    • H01M50/431—Inorganic material
    • H01M50/434—Ceramics
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
    • H01M50/409—Separators, membranes or diaphragms characterised by the material
    • H01M50/431—Inorganic material
    • H01M50/434—Ceramics
    • H01M50/437—Glass
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
    • H01M50/409—Separators, membranes or diaphragms characterised by the material
    • H01M50/449—Separators, membranes or diaphragms characterised by the material having a layered structure
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M2220/00—Batteries for particular applications
    • H01M2220/20—Batteries in motive systems, e.g. vehicle, ship, plane
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M2300/00—Electrolytes
    • H01M2300/0017—Non-aqueous electrolytes
    • H01M2300/0065—Solid electrolytes
    • H01M2300/0068—Solid electrolytes inorganic
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M2300/00—Electrolytes
    • H01M2300/0088—Composites
    • H01M2300/0094—Composites in the form of layered products, e.g. coatings
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
    • Y02P70/50—Manufacturing or production processes characterised by the final manufactured product

Definitions

  • the present invention relates to an alkali-ion conducting separator assembly comprising a porous membrane (A) and an alkali-ion conducting film (B) placed on one major surface of the porous membrane (A), wherein the alkali-ion conducting film (B) comprises an inorganic material of the general formula (I):
  • the present invention further relates to a process for producing such an alkali-ion conducting separator assembly and to a rechargeable electrochemical cell comprising such an alkali-ion conducting separator assembly.
  • Secondary batteries, accumulators or “rechargeable batteries” are just some embodiments by which electrical energy can be stored after generation and used when required. Owing to the significantly better power density, there has in recent times been a move away from the water- based secondary batteries toward development of those batteries in which the charge transport in the electrical cell is accomplished by lithium ions.
  • alkali metal-oxygen cells an alkali metal like lithium or sodium is oxidized with atmospheric oxygen in a non-aqueous electrolyte to form an oxide, a peroxide or a superoxide, i.e., to form U2O or L12O2 while in the course of charging the oxide, peroxide or superoxide ions are oxidized to oxygen.
  • the positively and negatively charged electrode compositions are mechanically separated from one another by layers which are not electrically conductive, known as separators, to avoid internal discharge. Due to their microporous structure many commonly used separators like polymer membranes or nonwovens do not only allow the transport of positive ionic charges like lithium cations as basic prerequisite for continuing offtake of current during operation of the electrochemical cell but also open the unwanted migration of polysulfide ions or reducible charged oxygen species from the cathode to the metal anode. In order to avoid these parasitic processes alternative separators have been discussed. Solid lithium electrolytes like solid Li-ion conductors have been proposed and investigated as separators in electrochemical cells.
  • US 8,323,817 describes a galvanic cell comprising a water-impermeable, alkali-ion-conductive ceramic membrane as separator.
  • US 2012/02701 12 describes a composite solid electrolyte that includes a monolithic solid electrolyte base component that is a continuous matrix of an inorganic active metal ion conductor and a filler component used to eliminate through porosity in the solid electrolyte.
  • WO2012/013603 describes an inorganic electrolyte membrane, wherein that membrane is a porous membrane made of an electrically insulating metal or metalloid oxide having through- pores or through-channels, which are open at the ends and wherein an electrolyte is confined within the pores of the membrane.
  • separators known from the literature which comprise alkali-ion conducting materials, still have deficiencies in respect of one or more of the properties desired for such separators, for example low thickness, low weight per unit area, good mechanical stability during processing or in operation of the battery in respect of metal dendrite growth, good heat resistance, good ion conductivity and complete impermeability for organic solvents.
  • Some of the deficiencies of the known separators are ultimately responsible for a reduced life or limited performance of the electrochemical cells comprising them.
  • separators in principle have to be not only mechanically but also chemically stable toward the cathode materials, the anode materials and the electrolytes. In the field of lithium-sulfur cells, separators which also prevent early cell death of lithium-sulfur cells, which is brought about particularly by migration of polysulfide ions from the cathode to the anode, are desirable.
  • an alkali-ion conducting separator assembly comprising
  • A a porous membrane (A), which consists of at least one inorganic, electrically insulating and non-alkali-ion conducting material, having through pores that extend from one major surface of the membrane to an opposing major surface, and
  • alkali-ion conducting film (B) placed on one major surface of the porous membrane (A), wherein the through pores of the porous membrane (A) are sealed by the alkali-ion conducting film (B), wherein the alkali-ion conducting film (B) comprises an inorganic material of the general formula (I)
  • L is an alkali metal, like Li, Na or K, preferably Li,
  • I is Mg, Al or Ga, preferably Al,
  • A is a lanthanide, preferably La,
  • a is an alkali metal, alkaline earth metal or a lanthanide, preferably Ba,
  • B is Nb or Ta, preferably Ta,
  • b is Nb, Ta, Zr, Hf, Ce, Y, W, Mo, Sb, Te, Bi, Sn, Ti or Pr, preferably Zr,
  • D is F (fluorine), S (sulfur), N (nitrogen) or C (carbon), m is 2 for Mg or 3 for Al or Ga,
  • n 1 for alkali metal, 2 for alkaline earth metal or 2, 3 or 4 for lanthanide,
  • p is 2, 3, 4, 5 or 6 depending on the oxidation state of metal b
  • v is 1 for F (fluorine), 2 for S (sulfur), 3 for N (nitrogen) or 4 for C (carbon),
  • w is in the range from 0 to 12, preferably in the range from 0 to 6, in particular 0 to 3
  • u is in the range from 0 to 12, preferably in the range from 0 to wv/2, in particular wv/2
  • x is in the range from 0 to 0.75, preferably in the range from 0.25 to 0.35, in particular 0.29
  • y is in the range from 0 to 3, preferably in the range from 0 to 1 ,
  • z is in the range from 0 to 2, preferably in the range from 0.5 to 1 .75.
  • Examples of a lanthanide are La, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb or Lu.
  • the inventive alkali-ion conducting separator assembly comprises at least two layers that means at least one porous membrane (A) and at least one alkali-ion conducting film (B) as described above.
  • the thickness of the inventive alkali-ion conducting separator assembly can be varied in a wide range.
  • the inventive alkali-ion conducting separator assembly has an average thickness in the range from 1 to 1000 ⁇ , preferably in the range from 5 to 500 ⁇ , in particular in the range from 5 to 100 ⁇ .
  • the inventive alkali-ion conducting separator assembly preferably consists of one porous membrane (A) that is sealed on one side with one or more, preferably with one alkali-ion conducting film (B).
  • the porous membrane (A) which consists of at least one inorganic, electrically insulating and non-alkali-ion conducting material, has through pores that extend from one major surface of membrane (A) to an opposing major surface.
  • the porous membrane (A) itself is electrically insulating.
  • the porous membrane (A) consists of one inorganic, electrically insulating and non-alkali-ion conducting material.
  • electrically insulating means, that the electrical conductivity of the material is less than 10 8 S/cm at 25 °C.
  • the inorganic, electrically insulating and non-alkali-ion conducting material can be chosen from a wide range of suitable materials known to the person skilled in the art.
  • a preferred material is selected from the group consisting of ceramics, sintered ceramics, glass-ceramics and glasses, preferably ceramics.
  • Preferred ceramics are chosen from the group consisting of Si0 2 , AI2O3, MgO, MgAI 2 0 4 , Ti0 2 , Zr0 2 , SiC and Si3N 4 , preferably Si0 2 , AI 2 C>3 and MgO, particularly preferred Si0 2 and AI 2 C>3, in particular AI 2 C>3.
  • the alkali-ion conducting separator assembly is characterized in that the inorganic, electrically insulating and non-alkali-ion conducting material of the porous membrane (A) is selected from the group consisting of ceramics, sintered ceramics, glass-ceramics and glasses, preferably ceramics, in particular anodically oxidized aluminum (anodized aluminum oxide (AAO), AI 2 C>3).
  • AAO anodically oxidized aluminum oxide
  • AI 2 C AI 2 C>3
  • AAO anodically oxidized aluminum
  • the thickness of the porous membrane (A) can be varied in a wide range.
  • the porous membrane (A) has an average thickness in the range from 1 to 1000 ⁇ , preferably in the range from 5 to 500 ⁇ , in particular in the range from 5 to 100 ⁇ .
  • the alkali-ion conducting separator assembly is characterized in that the porous membrane (A) has an average thickness in the range from 5 to 500 ⁇ .
  • the average diameter of the through pores of the porous membrane (A) can be varied in a wide range.
  • the average diameter of the through pores is in the range from 0.01 to 100 ⁇ , preferably in the range from 0.02 to 10 ⁇ , in particular in the range from 0.04 to 0.4 ⁇ .
  • the porosity of the porous membrane (A) can be varied in a wide range.
  • the porosity of the porous membrane (A) is in the range from 10 to 90%, more preferably in the range from 15 to 75%, in particular in the range from 20 to 60% by volume based on the total volume of the membrane.
  • the alkali-ion conducting film (B), which is placed on one major surface of the porous membrane (A), in order to seal the through pores of the porous membrane (A), comprises an inorganic material of the general formula (I) as described above.
  • L is Li, I is Al, A is La, a is Ba, B is Ta, b is Zr, m is 3, n is 2, p is 4, x is in the range from 0 to 0.75, y is in the range from 0 to 3, z is in the range from 0 to 2, w is 0 and u is 0.
  • Examples of preferred compounds are for example Li6BaLa2Ta20i2,
  • the thickness of the alkali-ion conducting film (B) can be varied in a wide range.
  • the alkali-ion conducting film (B) has an average thickness in the range from 0.01 to 1000 ⁇ , preferably in the range from 0.01 to 40 ⁇ , in particular in the range from 0.05 to 4 ⁇ .
  • the alkali-ion conducting separator assembly is characterized in that the alkali-ion conducting film (B) has an average thickness in the range from 0.01 to 40 ⁇ , preferably in the range from 0.05 to 4 ⁇ .
  • the alkali-ion conducting film (B) consists of at least 80% by weight, preferably at least 90% by weight, in particular in the range from 95% to 100% by weight of at least one, preferably one or two, in particular one inorganic material of the general formula (I).
  • the thickness of the porous membrane (A) and of the alkali-ion conducting film (B) as well as the average diameter of the through pores of the porous membrane (A) can be determined according to Scanning Electron Microscopy (SEM, cross section analysis) or Transmission Electron Microscopy (TEM) measurement.
  • the alkali-ion conducting film (B) is impermeable to organic solvents. Therefore the alkali-ion conducting separator assembly is also impermeable to organic solvents.
  • the alkali-ion conducting separator assembly is characterized in that the alkali-ion conducting separator assembly is impermeable to organic solvents.
  • the present invention further provides a process for producing an alkali-ion conducting separator assembly comprising (A) a porous membrane (A), which consists of at least one inorganic, electrically insulating and non-alkali-ion conducting material, having through pores that extend from one major surface of the membrane to an opposing major surface, and
  • alkali-ion conducting film (B) placed on one major surface of the porous membrane (A), wherein the through pores of the porous membrane (A) are sealed by the alkali-ion conducting film (B), wherein the alkali-ion conducting film (B) comprises an inorganic material of the general formula (I)
  • L is an alkali metal, like Li, Na or K, preferably Li,
  • I is Mg, Al or Ga, preferably Al,
  • A is a lanthanide, preferably La,
  • a is an alkali metal, alkaline earth metal or a lanthanide, preferably Ba,
  • B is Nb or Ta, preferably Ta,
  • b is Nb, Ta, Zr, Hf, Ce, Y, W, Mo, Sb, Te, Bi, Sn, Ti or Pr, preferably Zr,
  • D is F (fluorine), S (sulfur), N (nitrogen) or C (carbon), m is 2 for Mg or 3 for Al or Ga,
  • n 1 for alkali metal, 2 for alkaline earth metal or 2, 3 or 4 for lanthanide,
  • p is 2, 3, 4, 5 or 6 depending on the oxidation state of metal b
  • v is 1 for F (fluorine), 2 for S (sulfur), 3 for N (nitrogen) or 4 for C (carbon),
  • w is in the range from 0 to 12, preferably in the range from 0 to 6, in particular 0 to 3
  • u is in the range from 0 to 12, preferably in the range from 0 to wv/2, in particular wv/2
  • x is in the range from 0 to 0.75, preferably in the range from 0.25 to 0.35, in particular 0.29
  • y is in the range from 0 to 3, preferably in the range from 0 to 1 ,
  • z is in the range from 0 to 2, preferably in the range from 0.5 to 1 .75, comprising the process step of
  • a layer of a material which is alkali-ion conducting or which becomes alkali-ion conducting after thermal or chemical, preferably thermal treatment, on one major surface of a porous membrane (A), which consists of inorganic, electrically insulating and non- alkali-ion conducting material, having through pores that extend from one major surface of the membrane to an opposing major surface, and (b) optionally calcination of the porous membrane with the deposited layer formed in process step (a) in a temperature range from 100 °C to 1500 °C, preferably in a temperature range from 500 to 900 °C.
  • alkali-ion conducting separator assembly and its components, in particular the description of the porous membrane (A) as a first component and of the alkali-ion conducting film (B) as a second component, in the process of the invention correspond to the above description of these components for the alkali-ion conducting separator assembly of the invention.
  • a layer of a material which is alkali-ion conducting or which becomes alkali- ion conducting after thermal or chemical, preferably thermal treatment, is deposited on one major surface of a porous membrane (A), which consists of inorganic, electrically insulating and non-alkali-ion conducting material, having through pores that extend from one major surface of the membrane to an opposing major surface.
  • the layer of the material which is alkali-ion conducting or which becomes alkali-ion conducting after thermal or chemical, preferably thermal treatment, preferably comprises at least one inorganic material of the general formula (I):
  • the layer of the material consists of at least 80% by weight, preferably at least 90% by weight, in particular in the range from 95% to 100% by weight of at least one, preferably one or two, in particular one inorganic material of the general formula (I).
  • Preferred deposition methods are pulsed laser deposition (PLD), physical vapor deposition (PVD), chemical vapor deposition (CVD), sputter techniques or (spray) casting methods (spraying/dip coating/sol-gel).
  • PLD pulsed laser deposition
  • PVD physical vapor deposition
  • CVD chemical vapor deposition
  • sputter techniques sputter techniques
  • spray spray casting methods
  • the inventive process is characterized in that in process step (a) the material, which is alkali-ion conducting or which becomes alkali-ion conducting after thermal or chemical, preferably thermal treatment, is deposited on the surface of the porous membrane (A) by pulsed laser deposition (PLD).
  • PLD pulsed laser deposition
  • the deposited layer of the material which is alkali-ion conducting or which becomes alkali-ion conducting after thermal or chemical, preferably thermal treatment, forms a film, that is alkali-ion conducting or becomes alkali-ion conducting after thermal or chemical, in particular thermal treatment, and that seals the through pores of the porous membrane (A) on one major surface of said membrane (A).
  • the porous membrane with the deposited layer formed in process step (a) is calcined in a temperature range from 100 °C to 1500 °C, preferably in a temperature range from 500 °C to 900 °C.
  • the calcination step can remove possible inhomogenei- ties in the layer of the material which are caused by the deposition method and might convert the deposited material from a non-alkali-ion conducting form to an alkali-ion conducting form. Inhomogeneities can be related to differences in the thickness or to the evenness of the layer or to the chemical or structural composition of the layer.
  • the calcination step might for example also convert the crystal structure of the deposited material.
  • the deposited layer formed in process step (a) can be treated chemically in order to modify the deposited material.
  • Possible methods of chemical treatment of the deposited layer include gas phase reactions (e.g. N2, N H3, N y O x , H2S, H2O, O2, H2, F2, HF, CI2, HCI and combinations of two or more aforementioned gases with defined partial pressures), reaction with molten chemical compounds or molten elements (e.g. (Li/Na)OH, (Li/Na)20, (Li/Na)NC>3 or Li/Na), reaction with evaporated chemical compounds or elements (e.g.
  • alkali-ion containing e.g. (Li/Na)OH, (Li/Na)20, (Li/Na)N0 3 , (Li/Na)(B/AI)H 4
  • alkali-ion free compounds e.g. H 2 0 2 , N 2 H 4 , NH 3 , HN0 3 / H NO2, H2S, H2SC , H2SO3
  • plasma treatment e.g.
  • the layer deposited in process step (a) and possibly further chemically or thermally treated forms the alkali-ion conducting film (B) of the inventive alkali-ion conducting separator assembly.
  • inventive alkali-ion conducting separator assemblies are particularly suitable as separator or as constituent of a separator in electrochemical cells, in particular in rechargeable electrochemical cells.
  • the term electrochemical cell or battery encompasses batteries, capacitors and accumulators (secondary batteries) of any type, in particular alkali metal cells or batteries such as lithium, lithium ion, lithium-sulfur, alkali metal-oxygen and alkaline earth metal batteries and accumulators, including in the form of high-energy or high-power systems, and also electrolyte capacitors and double-layer capacitors which are known under the names Supercaps, Goldcaps, BoostCaps or Ultracaps.
  • the present invention further provides a rechargeable electrochemical cell comprising at least one alkali-ion conducting separator assembly as described above.
  • the alkali-ion conducting separator assemblies of the invention are preferably suitable for electrochemical cells which are based on the transfer of alkali metal ions, in particular for lithium metal, lithium-sulfur, alkali metal-oxygen and lithium ion cells or batteries and especially for lithium ion secondary cells or secondary batteries.
  • the alkali-ion conducting separator assemblies of the invention are particularly suitable for rechargeable electrochemical cells from the group of lithium-sulfur cells and alkali metal-oxygen cells.
  • the present invention further provides a rechargeable electrochemical cell comprising
  • suitable cathode materials suitable anode materials, suitable electrolytes and possible arrangements
  • suitable monographs and reference works e.g. Wakihara et al. (editor): Lithium ion Batteries, 1 st edition, Wiley VCH, Weinheim, 1998; David Linden: Handbook of Batteries (McGraw-Hill Handbooks), 3 rd edition, Mcgraw-Hill Professional, New York 2008; J. O. Besenhard: Handbook of Battery Materials. Wiley-VCH, 1998.
  • the electrode where during discharging a net positive charge occurs is called the cathode.
  • the inventive rechargeable electrochemical cell comprises at least one cathode (a).
  • cathodes are, in particular, cathodes in which the cathode material comprises a lithium- transition metal oxide, e.g. lithium-cobalt oxide, lithium-nickel oxide, lithium-cobalt-nickel oxide, lithium-manganese oxide (spinel), lithium-nickel-cobalt-aluminum oxide, lithium-nickel-cobalt- manganese oxide or lithium-vanadium oxide, a lithium sulfide or lithium polysulfide such as U2S, L12S8, L12S6, L12S4 or L12S3 or a lithium-transition metal phosphate such as lithium-iron phosphate as electroactive constituent.
  • a lithium- transition metal oxide e.g. lithium-cobalt oxide, lithium-nickel oxide, lithium-cobalt-nickel oxide, lithium-manganese oxide (spinel), lithium-nickel-cobalt-aluminum
  • Cathode materials which comprise iodine, oxygen, sulfur and the like as electroactive constituent are also suitable. However, if materials comprising sulfur or po- lymers comprising polysulfide bridges are to be used as cathode materials, it has to be ensured that the anode is charged with Li° before such an electrochemical cell can be discharged and recharged.
  • lithium can be directly deposited (e.g. vapor deposition preferably sputtering, thermal vapor deposition or pulsed laser deposition, in particular thermal vapor deposition) on the open surface of the alkali-ion conducting film (B), which is placed with its opposite surface on the porous membrane (A).
  • Gas diffusion electrodes which are permeable to oxidizing gases, in particular to molecular oxygen O2, are known and used as cathodes in alkali metal-oxygen cells.
  • the alkali-ion conducting separator assembly is preferably used in inventive rechargeable electrochemical cells, wherein the at least one cathode (a) comprises an electro- active chalcogen-containing material, preferably an oxygen- or sulfur-containing material, in particular elemental sulfur.
  • the inventive rechargeable electrochemical cell is characterized in that the at least one cathode (a) comprises an electroactive chalcogen- containing material, preferably an oxygen- or sulfur-containing material, in particular elemental sulfur.
  • Cathode (a) may comprise one or further constituents.
  • cathode (a) may comprise carbon in an electrical conductive polymorph, for example selected from graphite, carbon black, carbon nanotubes, graphene or mixtures of at least two of the aforementioned substances.
  • cathode (a) may comprise one or more binders, for example one or more organic polymers. Suitable binders may be selected, for example, from those binders which are described in WO 201 1/161598, page 6, line 28 to page 8, line 15, where the binder is referred to as polymer (C) or binder (C).
  • Particularly suitable binders for the cathode (a) are especially polyvinyl alcohol and halogenated (co)polymers, for example polyvinyl chloride or polyvinylidene chloride, especially fluorinated (co)polymers such as polyvinyl fluoride and especially polyvinylidene fluoride and
  • cathode (a) may have further constituents customary per se, for example an output conductor, which may be configured in the form of a metal wire, metal grid, metal mesh, expanded metal, metal sheet or metal foil. Suitable metal foils are especially aluminum foils.
  • cathode (a) has a thickness in the range from 25 to 200 ⁇ , preferably from 30 to 100 ⁇ , based on the thickness without output conductor.
  • the inventive rechargeable electrochemical cell further comprises, as well as the inventive alkali-ion conducting separator assembly and the cathode (a), at least one anode (b).
  • the electrode where during discharging a net negative charge occurs is called the anode.
  • anode (b) can be selected from among anodes composed of carbon, anodes comprising Sn or Si, anodes comprising lithium titanate of the formula Li4+xTisOi2 in which x is a numerical value from > 0 to 3, and anodes comprising an alkali metal, preferably lithium or sodium, in particular lithium.
  • Anodes composed of carbon can, for example, be selected from among hard carbon, soft carbon, graphene, graphite and in particular graphite, intercalated graphite and mixtures of two or more of the abovementioned carbons.
  • Anodes comprising Sn or Si can, for example be selected from among nanoparticulate Si or Sn powder, Si or Sn fibers, carbon-Si or carbon-Sn composites and Si-metal or Sn-metal alloys.
  • the alkali metal preferably lithium or sodium, in particular lithium, may be present in the form of pure alkali metal or in the form of an alloy of an alkali metal with at least another metal or in the form of an alkali metal carbon intercalation compound.
  • the alkali-ion conducting separator assembly is preferably used in inventive rechargeable electrochemical cells, wherein the at least one anode (b) comprises an alkali metal, preferably lithium or sodium, in particular lithium.
  • the inventive rechargeable electrochemical cell is characterized in that the at least one anode (b) comprises an alkali metal, preferably lithium or sodium, in particular lithium.
  • the at least one anode (b) comprises an alkali metal, preferably lithium or sodium, in particular lithium.
  • the at least one anode (b) comprises an alkali metal, preferably lithium or sodium, in particular lithium.
  • the at least one anode (b) comprises an alkali metal, preferably lithium or sodium, in particular lithium.
  • anode (b) can also comprise further constituents, for example
  • electrically conductive or electroactive constituents such as carbon black, graphite, carbon fibers, carbon nanofibers, carbon nanotubes or electrically conductive polymers;
  • binders such as polyethylene oxide (PEO), cellulose, carboxymethylcellulose (CMC), polyethylene, polypropylene, polytetrafluoroethylene, polyacrylonitrile-methyl methacrylate, polyvinyl alcohol, polytetrafluoroethylene, styrene-butadiene copolymers, tetrafluoroeth- ylene-hexafluoroethylene copolymers, polyvinylidene difluoride (PVdF), polyvinylidene difluoride-hexafluoropropylene copolymers (PVdF-HFP), tetrafluoroethylene-hexa- fluoropropylene copolymers, tetrafluoroethylene, perfluoroalkyl-vinyl ether copolymers, vinylidene fluoride-hexafluoropropylene copolymers, ethylene-tetrafluoroethylene copolymers, vinylidene fluoride-
  • anode (b) may have further constituents customary per se, for example an output conductor which may be configured in the form of a metal wire, metal grid, metal mesh, expanded metal, or a metal foil or metal sheet. Suitable metal foils are especially copper foils.
  • anode (b) has a thickness in the range from 15 to 200 ⁇ , preferably from 30 to 100 ⁇ , based on the thickness without output conductor.
  • the inventive rechargeable electrochemical cell further comprises, as well as the inventive alkali-ion conducting separator assembly, the cathode (a) and the anode (b), at least one electrolyte composition (c) comprising
  • Possible aprotic organic solvents (c1 ) may be liquid or solid at room temperature and are preferably liquid at room temperature.
  • Solvents (c1 ) are preferably selected from polymers, cyclic or noncyclic ethers, cyclic or noncyclic acetals, cyclic or noncyclic organic carbonates and ionic liquids.
  • the inventive rechargeable electrochemical cell is characterized in that the aprotic organic solvent (c1 ) is selected from polymers, cyclic or noncyclic ethers, noncyclic or cyclic acetals and cyclic or noncyclic organic carbonates.
  • the aprotic organic solvent (c1 ) is selected from polymers, cyclic or noncyclic ethers, noncyclic or cyclic acetals and cyclic or noncyclic organic carbonates.
  • suitable polymers are especially polyalkylene glycols, preferably poly-Ci-C4- alkylene glycols and especially polyethylene glycols.
  • Polyethylene glycols may comprise up to 20 mol% of one or more Ci-C4-alkylene glycols in copolymerized form.
  • Polyalkylene glycols are preferably doubly methyl- or ethyl-capped polyalkylene glycols.
  • the molecular weight M w of suitable polyalkylene glycols and especially of suitable polyethylene glycols may be at least 400 g/mol.
  • the molecular weight M w of suitable polyalkylene glycols and especially of suitable polyethylene glycols may be up to 5 000 000 g/mol, preferably up to 2 000 000 g/mol.
  • noncyclic ethers are, for example, diisopropyl ether, di-n-butyl ether, 1 ,2- dimethoxyethane, 1 ,2-diethoxyethane, preference being given to 1 ,2-dimethoxyethane.
  • Suitable cyclic ethers are tetrahydrofuran and 1 ,4-dioxane.
  • noncyclic acetals are, for example, dimethoxymethane, diethoxymethane, 1 ,1 -dimethoxyethane and 1 ,1 -diethoxyethane.
  • Suitable cyclic acetals are 1 ,3-dioxane and especially 1 ,3-dioxolane.
  • suitable noncyclic organic carbonates are dimethyl carbonate, ethyl methyl carbonate and diethyl carbonate.
  • Suitable cyclic organic carbonates are compounds of the general formulae (X) and (XI)
  • R 1 , R 2 and R 3 may be the same or different and are each selected from hydrogen and Ci-C4-alkyl, for example methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl and tert- butyl, where R 2 and R 3 are preferably not both tert-butyl.
  • R 1 is methyl and R 2 and R 3 are each hydrogen, or R 1 , R 2 and R 3 are each hydrogen.
  • Another preferred cyclic organic carbonate is vinylene carbonate, formula (XII).
  • Possible alkali metal salts (c2) which are used as conductive salts, have to be soluble in the aprotic organic solvent (c1 ).
  • Preferred alkali metal salts (c2) are lithium salts or sodium salts, in particular lithium salts.
  • the inventive rechargeable electrochemical cell is characterized in that wherein the alkali metal salt (c2) is a lithium salt or sodium salt, preferably a lithium salt.
  • the alkali metal salt (c2) is a lithium salt or sodium salt, preferably a lithium salt.
  • Suitable alkali metal salts are especially lithium salts. Examples of suitable lithium salts are
  • LiPF 6 , LiBF 4 , L1CIO4, LiAsFe, UCF3SO3, LiC(C n F 2 n + iS0 2 )3, lithium imides such as
  • LiN(CnF2n+iSC>2)2 where n is an integer in the range from 1 to 20, LiN(SC>2F)2, Li2SiF6, LiSbF6,
  • LiAICU LiAICU, and salts of the general formula (C n F2n+iS02) m XLi, where m is defined as follows:
  • m 3 when X is selected from carbon and silicon.
  • Preferred alkali metal salts are selected from LiC(CF 3 S0 2 )3, LiN(CF 3 S0 2 ) 2 , LiPF 6 , LiBF 4 , L1CIO4, and particular preference is given to LiPF6 and LiN(CF3SC>2)2.
  • the through pores of the porous membrane (A), which are open on the major side opposite to the sealing alkali-ion conducting film (B) can be filled either with suitable cathode materials, suitable anode materials or suitable electrolytes.
  • the pores of the porous membrane (A) are filled with electrolyte composition (c) as described above.
  • the inventive rechargeable electrochemical cell is characterized in that the alkali-ion conducting separator assembly comprises one porous, inorganic, non-alkali-ion conducting membrane (A) having through pores that extend from one major surface of the membrane to an opposing major surface, wherein an alkali-ion conducting film (B) is placed on one major surface of the porous, inorganic, non-alkali-ion conducting membrane (A) and the porous membrane (A) is filled with electrolyte composition (c).
  • the alkali-ion conducting separator assembly comprises one porous, inorganic, non-alkali-ion conducting membrane (A) having through pores that extend from one major surface of the membrane to an opposing major surface, wherein an alkali-ion conducting film (B) is placed on one major surface of the porous, inorganic, non-alkali-ion conducting membrane (A) and the porous membrane (A) is filled with electrolyte composition (c).
  • inventive rechargeable electrochemical cells further comprise a housing which may be of any shape, for example cuboidal or in the shape of a cylinder. In another embodiment, inventive rechargeable electrochemical cells have the shape of a prism. In one variant, the housing used is a metal-plastic composite film processed as a pouch.
  • the inventive rechargeable electrochemical cells can be assembled to rechargeable batteries, preferably rechargeable alkali metal ion batteries like lithium ion batteries, lithium sulfur batteries, lithium air batteries or sodium air batteries, in particular lithium sulfur batteries.
  • rechargeable batteries preferably rechargeable alkali metal ion batteries like lithium ion batteries, lithium sulfur batteries, lithium air batteries or sodium air batteries, in particular lithium sulfur batteries.
  • the present invention also further provides for the use of inventive rechargeable electrochemical cells as described above in rechargeable batteries, especially rechargeable lithium sulfur batteries.
  • the present invention further provides an alkali metal ion battery comprising at least one rechargeable electrochemical cell as described above.
  • inventive rechargeable electrochemical cells can be combined with one another in inventive alkali metal ion batteries, for example in series connection or in parallel connection. Series connection is preferred.
  • Inventive rechargeable electrochemical cells are notable for particularly high capacities, high performances even after repeated charging and greatly retarded cell death.
  • Inventive rechargeable electrochemical cells are very suitable for use in motor vehicles, bicycles operated by electric motor (e.g. pedelecs), aircraft, ships and boats or stationary energy storage. Such uses form a further part of the subject matter of the present invention.
  • the present invention further provides for the use of inventive rechargeable electrochemical cells as described above in motor vehicles, bicycles operated by electric motor, aircraft, ships and boats or stationary energy storage.
  • inventive rechargeable electrochemical cells in devices gives the advantage of prolonged run time before recharging and a smaller loss of capacity in the course of prolonged run time. If the intention were to achieve an equal run time with electrochemical cells with lower energy density, a higher weight for electrochemical cells would have to be accepted.
  • the present invention therefore further provides for the use of inventive rechargeable electrochemical cells in devices, especially in mobile devices.
  • mobile devices are vehicles, for example automobiles, bicycles, aircraft, or water vehicles such as boats or ships.
  • Other examples of mobile devices are those which are portable, for example computers, especially laptops, telephones or electrical power tools, for example from the construction sector, especially drills, battery-driven screwdrivers or battery-driven tackers.
  • the present invention further provides a device comprising at least one rechargeable electrochemical cell as described above.
  • Li6BaLa2Ta20i2 as target material for pulsed laser deposition was prepared by solid state reaction according to J. Awaka, N. Kijima, H. Hayakawa and J. Akimoto, Journal of Solid State Chemistry, 2009, 182, 2046.
  • Li6BaLa2Ta20i2 on anodized aluminum oxide (AAO) membrane Li6BaLa2Ta20i2 on anodized aluminum oxide (AAO) membrane
  • the deposition of lithium ion conducting garnet-type material on top of porous AAO was carried out by pulsed laser deposition (PLD).
  • PLD pulsed laser deposition
  • the PLD (Surface GmbH & Co. KG, Frankfurt am Main, Germany) was directly attached to an argon gas filled glove box (M. Braun GmbH, Garching, Germany) to avoid air contact of the samples.
  • Li6BaLa2Ta20i2 was used as target.
  • An AAO disc AlporeTM inorganic membrane (AnodiscTM) by Whatman pic, Maidstone, Kent, UK) with a diameter of 13 mm, average pore size of 100 nm and thickness of 60 ⁇ was used as a sub- strate.
  • a KrF Excimer Laser (Compex 201 F, Coherent Inc., Santa Clara, CA, USA) with a wavelength of 248 nm was used for the deposition of the garnet-type thin films.
  • the PLD chamber Prior to ablation the PLD chamber was evacuated to 1 x10 -5 mbar. The deposition process took place in pure 5x10 -2 mbar oxygen atmosphere (higher and lower pressure values were also possible, e.g. deposition at 2x10 "2 mbar oxygen atmosphere was also possible).
  • the distance between target and substrate was set to 45 mm.
  • this parameter (distance), which could be adjusted from 40 mm - 85 mm, had little to no influence on the crystal structure of the deposited material but that it had a bigger influence on the deposition rate and film morphology.
  • the substrate was attached to a metallic substrate holder by a mask with a hole of 12 mm and the substrate holder was heated to 840 °C by an IR-laser heater.
  • this temperature is the temperature measured at the backside of the substrate holder with a Pyrometer and was not the surface temperature of the substrate.
  • the surface temperature of the substrate was believed to be in the range from 500 °C - 800 °C.
  • the type of heater, IR-Laser or any other type of heat source is not relevant.
  • the laser fluence was adjusted in the range from 2 J/cm 2 to 4 J/cm 2 .
  • the laser frequency was adjusted to 10 Hz wherein the laser frequency has an influence on the deposition rate.
  • the thin films had thicknesses between 0.5 ⁇ and 3 ⁇ .
  • Substrate AAO-disk from Whatman; diameter: 13 mm; pore sizes: 100 nm; thickness: 60 ⁇ .
  • Crystal structure cubic garnet-type phase (XRD, preferred orientation)
  • Figure 1 shows a SEM cross-section of SA.1 (LBLTO on AAO)
  • Li6.5La3Zr1.5Tao.5O12 was used as target in place of Li6BaLa2Ta20i2 to produce alkali-ion conducting separator assembly SA.2.
  • Li6.5La3Zr1.5Tao.5O12 was prepared according to J. Power Sources 2012, 236-244.
  • Substrate AAO-disk from Whatman; diameter: 13 mm; pore sizes: 100 nm; thickness: 60 ⁇ .
  • Target Chemical composition: Li6.5La3Zr1.5Tao.5O12
  • conductive carbon additives Printex XE2 (Orion) and Super C65 (TIMCALTM) in a ratio of 1 :1 ) and polyvinyl alcohol) (Aldrich) were mixed with mass ratio of 60:35:5 in water to form a slurry.
  • the slurry was then coated onto aluminum foil (20 ⁇ ) with a doctor ' s blade and dried in vacuum at 40 °C for 16 h.
  • the electrolyte was a solution of 12 wt% lithium bis(trifluromethanesulfonyl)imide (LiTFSI) (Aldrich, 99.95%), 44 wt% of 1 ,2-dimethoxyethane (DME) (Alfa Aesar, 99+%) and 44 wt% 1 ,3- dioxolane (DOL) (Acros, 99.8%).
  • LiTFSI lithium bis(trifluromethanesulfonyl)imide
  • DME 1 ,2-dimethoxyethane
  • DOL 1 ,3- dioxolane
  • the electrolyte solvents were purified by distillation from sodium potassium alloy under argon atmosphere.
  • a coin-type cell was assembled in an argon-filled glovebox using a sulfur cathode (a) with an electrode diameter of 8 mm, the alkali-ion conducting separator assembly SA.1 produced according to 1.1 (diameter of (A) 13 mm and (B) 12 mm, respectively) and lithium foil (China Lithium Ltd., 600 ⁇ , 8 mm) as negative electrode (anode (b)). Additionally a glass fiber separator (GF/A, Whatman) was placed between anode (b) and the Li-ion conductive film (B). The cathode electrode (a) was assembled on the opposite side of the Li-ion conductive film (B) and directly on the porous membrane (A). The glass fiber separator (C) and positive electrode (a) were soaked with electrolyte (c).
  • Discharge-charge cycling of the cell was performed at 0.036 mA (corresponds to a rate of C/50 for the used cathode electrode) for the first cycle with a discharge cutoff voltage of 1.7 V and charge cutoff at 2.5 V.
  • a discharge current of 0.36 mA, and charge current of 0.22 mA was applied. This corresponds to a discharge rate of C/5 and a charge rate of C/8 for this cell.
  • the electrochemical experiments were carried out under controlled and constant environmental conditions.
  • Figure 2 shows the schematic structure of the different layers of the electrochemical cell EC.1.
  • the annotations in Figure 2 mean:
  • Figure 3 shows the voltage profile of the Li/S cell EC.1. Plotted are the first cycle with an applied current of 0.036 mA for charge and discharge, and the second cycle with a discharged current of 0.36 mA and charge current of 0.22 mA.
  • Figure 4 shows the electrochemical performance of the Li/S cell EC.1 .
  • a coin-type cell was assembled in an argon-filled glovebox using a sulfur cathode (a) with an electrode diameter of 8 mm and the alkali-ion conducting separator assembly SA.1 produced according to 1.1 (diameter of (A) 13 mm and (B) 12 mm, respectively), wherein a layer of lithium
  • Figure 5 shows the schematic structure of the different layers of the electrochemical cell EC.2.
  • the annotations in Figure 5 mean:

Landscapes

  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Manufacturing & Machinery (AREA)
  • Inorganic Chemistry (AREA)
  • Materials Engineering (AREA)
  • Ceramic Engineering (AREA)
  • Secondary Cells (AREA)
  • Cell Separators (AREA)

Abstract

The present invention relates to an alkali-ion conducting separator assembly comprising a porous membrane (A) and an alkali-ion conducting film (B) placed on one major surface of the porous membrane (A), wherein the alkali-ion conducting film (B) comprises an inorganic material of the general formula (I): (L1+[(12-u)2 + wv]-xm-[(3-y)3+yn]-[(2-z)5+zp] Im+x ) (A3+3-y an+y) (B5+2-z bp+z) (O2-12-υ Dv-w) (I). The present invention further relates to a process for producing such an alkali-ion conducting separator assembly and to a rechargeable electrochemical cell comprising such an alkali-ion conducting separator assembly.

Description

Alkali-ion conductive separator assembly for rechargeable electrochemical cells Description
The present invention relates to an alkali-ion conducting separator assembly comprising a porous membrane (A) and an alkali-ion conducting film (B) placed on one major surface of the porous membrane (A), wherein the alkali-ion conducting film (B) comprises an inorganic material of the general formula (I):
(L1 +[(12-U)2 + wV]-xm-[(3-y)3+yn]-[(2-z)5+zp] lm+x ) (A3+3-y an+ y) (B5+2-z b + z) (02 2-υ Dv" w) (I).
The present invention further relates to a process for producing such an alkali-ion conducting separator assembly and to a rechargeable electrochemical cell comprising such an alkali-ion conducting separator assembly.
Secondary batteries, accumulators or "rechargeable batteries" are just some embodiments by which electrical energy can be stored after generation and used when required. Owing to the significantly better power density, there has in recent times been a move away from the water- based secondary batteries toward development of those batteries in which the charge transport in the electrical cell is accomplished by lithium ions.
However, the energy density of conventional lithium ion accumulators which have a carbon anode and a cathode based on metal oxides is limited. New horizons with regard to energy density have been opened up by lithium-sulfur cells and by alkali metal-oxygen cells. In lithium- sulfur cells, sulfur is reduced in the sulfur cathode via polysulfide ions to S2_ which on charging of the cell is reoxidized to form sulfur-sulfur bonds. In alkali metal-oxygen cells an alkali metal like lithium or sodium is oxidized with atmospheric oxygen in a non-aqueous electrolyte to form an oxide, a peroxide or a superoxide, i.e., to form U2O or L12O2 while in the course of charging the oxide, peroxide or superoxide ions are oxidized to oxygen.
In electrochemical cells, the positively and negatively charged electrode compositions are mechanically separated from one another by layers which are not electrically conductive, known as separators, to avoid internal discharge. Due to their microporous structure many commonly used separators like polymer membranes or nonwovens do not only allow the transport of positive ionic charges like lithium cations as basic prerequisite for continuing offtake of current during operation of the electrochemical cell but also open the unwanted migration of polysulfide ions or reducible charged oxygen species from the cathode to the metal anode. In order to avoid these parasitic processes alternative separators have been discussed. Solid lithium electrolytes like solid Li-ion conductors have been proposed and investigated as separators in electrochemical cells. Basic requirements, which such separators have to meet, are chemical and electrochemical stability toward both the active electrode compositions, resistance to dendrite growth and high cell temperatures, impermeability for mobile electrode components and liquid electrolyte components, and high ion conductivity even at room temperature and below. WO 2005/085138 and WO2009/003695 describe several ion conductors having a garnet structure.
Abstract # 316, 223rd. ECS Meeting 2013 describes aluminum migration during deposition of Li7La3Zr20i2 thin films on aluminum oxide substrates.
US 8,323,817 describes a galvanic cell comprising a water-impermeable, alkali-ion-conductive ceramic membrane as separator.
US 2012/02701 12 describes a composite solid electrolyte that includes a monolithic solid electrolyte base component that is a continuous matrix of an inorganic active metal ion conductor and a filler component used to eliminate through porosity in the solid electrolyte.
WO2012/013603 describes an inorganic electrolyte membrane, wherein that membrane is a porous membrane made of an electrically insulating metal or metalloid oxide having through- pores or through-channels, which are open at the ends and wherein an electrolyte is confined within the pores of the membrane.
The separators known from the literature, which comprise alkali-ion conducting materials, still have deficiencies in respect of one or more of the properties desired for such separators, for example low thickness, low weight per unit area, good mechanical stability during processing or in operation of the battery in respect of metal dendrite growth, good heat resistance, good ion conductivity and complete impermeability for organic solvents. Some of the deficiencies of the known separators are ultimately responsible for a reduced life or limited performance of the electrochemical cells comprising them. Furthermore, separators in principle have to be not only mechanically but also chemically stable toward the cathode materials, the anode materials and the electrolytes. In the field of lithium-sulfur cells, separators which also prevent early cell death of lithium-sulfur cells, which is brought about particularly by migration of polysulfide ions from the cathode to the anode, are desirable.
It was therefore an object of the invention to provide an inexpensive separator for a long-lived electrochemical cell, in particular a lithium-sulfur cell or an alkali metal-oxygen cell, which has advantages in respect of one or more properties of a known separator, in particular a separator which displays sufficient ion conductivity, high thermal stability and good mechanical properties.
This object is achieved by an alkali-ion conducting separator assembly comprising
(A) a porous membrane (A), which consists of at least one inorganic, electrically insulating and non-alkali-ion conducting material, having through pores that extend from one major surface of the membrane to an opposing major surface, and
(B) an alkali-ion conducting film (B) placed on one major surface of the porous membrane (A), wherein the through pores of the porous membrane (A) are sealed by the alkali-ion conducting film (B), wherein the alkali-ion conducting film (B) comprises an inorganic material of the general formula (I)
(L1 +[(12-U)2 + wV]-xm-[(3-y)3+yn]-[(2-z)5+zp] lm+x ) (A3+3-y an+ y) (B5+2-z b + z) (02 2-υ DV" W) (I) in which the variables are each defined as follows:
L is an alkali metal, like Li, Na or K, preferably Li,
I is Mg, Al or Ga, preferably Al,
A is a lanthanide, preferably La,
a is an alkali metal, alkaline earth metal or a lanthanide, preferably Ba,
B is Nb or Ta, preferably Ta,
b is Nb, Ta, Zr, Hf, Ce, Y, W, Mo, Sb, Te, Bi, Sn, Ti or Pr, preferably Zr,
D is F (fluorine), S (sulfur), N (nitrogen) or C (carbon), m is 2 for Mg or 3 for Al or Ga,
n is 1 for alkali metal, 2 for alkaline earth metal or 2, 3 or 4 for lanthanide,
p is 2, 3, 4, 5 or 6 depending on the oxidation state of metal b,
v is 1 for F (fluorine), 2 for S (sulfur), 3 for N (nitrogen) or 4 for C (carbon), w is in the range from 0 to 12, preferably in the range from 0 to 6, in particular 0 to 3, u is in the range from 0 to 12, preferably in the range from 0 to wv/2, in particular wv/2, x is in the range from 0 to 0.75, preferably in the range from 0.25 to 0.35, in particular 0.29, y is in the range from 0 to 3, preferably in the range from 0 to 1 ,
z is in the range from 0 to 2, preferably in the range from 0.5 to 1 .75.
Examples of a lanthanide are La, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb or Lu.
The inventive alkali-ion conducting separator assembly comprises at least two layers that means at least one porous membrane (A) and at least one alkali-ion conducting film (B) as described above. The thickness of the inventive alkali-ion conducting separator assembly can be varied in a wide range. Preferably the inventive alkali-ion conducting separator assembly has an average thickness in the range from 1 to 1000 μιτι, preferably in the range from 5 to 500 μιτι, in particular in the range from 5 to 100 μιτι.
The inventive alkali-ion conducting separator assembly preferably consists of one porous membrane (A) that is sealed on one side with one or more, preferably with one alkali-ion conducting film (B).
The porous membrane (A), which consists of at least one inorganic, electrically insulating and non-alkali-ion conducting material, has through pores that extend from one major surface of membrane (A) to an opposing major surface. The porous membrane (A) itself is electrically insulating. Preferably the porous membrane (A) consists of one inorganic, electrically insulating and non-alkali-ion conducting material.
In the context of the present invention the expression "electrically insulating" means, that the electrical conductivity of the material is less than 10 8 S/cm at 25 °C.
The inorganic, electrically insulating and non-alkali-ion conducting material can be chosen from a wide range of suitable materials known to the person skilled in the art. A preferred material is selected from the group consisting of ceramics, sintered ceramics, glass-ceramics and glasses, preferably ceramics. Preferred ceramics are chosen from the group consisting of Si02, AI2O3, MgO, MgAI204, Ti02, Zr02, SiC and Si3N4, preferably Si02, AI2C>3 and MgO, particularly preferred Si02 and AI2C>3, in particular AI2C>3.
In one embodiment of the present invention the alkali-ion conducting separator assembly is characterized in that the inorganic, electrically insulating and non-alkali-ion conducting material of the porous membrane (A) is selected from the group consisting of ceramics, sintered ceramics, glass-ceramics and glasses, preferably ceramics, in particular anodically oxidized aluminum (anodized aluminum oxide (AAO), AI2C>3).
The formation of controlled-porosity membranes from anodically oxidized aluminum (AAO) is known to the person skilled in the art.
The thickness of the porous membrane (A) can be varied in a wide range. Preferably the porous membrane (A) has an average thickness in the range from 1 to 1000 μιτι, preferably in the range from 5 to 500 μιτι, in particular in the range from 5 to 100 μιτι.
In one embodiment of the present invention the alkali-ion conducting separator assembly is characterized in that the porous membrane (A) has an average thickness in the range from 5 to 500 μιτι.
The average diameter of the through pores of the porous membrane (A) can be varied in a wide range. Preferably the average diameter of the through pores is in the range from 0.01 to 100 μιτι, preferably in the range from 0.02 to 10 μιτι, in particular in the range from 0.04 to 0.4 μιτι.
The porosity of the porous membrane (A) can be varied in a wide range. Preferably the porosity of the porous membrane (A) is in the range from 10 to 90%, more preferably in the range from 15 to 75%, in particular in the range from 20 to 60% by volume based on the total volume of the membrane. The alkali-ion conducting film (B), which is placed on one major surface of the porous membrane (A), in order to seal the through pores of the porous membrane (A), comprises an inorganic material of the general formula (I) as described above.
Particularly preferred is an inorganic material of the general formula (I) wherein
L is Li, I is Al, A is La, a is Ba, B is Ta, b is Zr, m is 3, n is 2, p is 4, x is in the range from 0 to 0.75, y is in the range from 0 to 3, z is in the range from 0 to 2, w is 0 and u is 0.
Examples of preferred compounds are for example Li6BaLa2Ta20i2,
Li5.755Alo.29La3Tao.375Zri.6250i2 or Li6.5La3Tao.5Zr1.5O12.
The preparation of the inorganic materials of the general formula (I) is known to the person skilled in the art and is for example described in WO 2005/085138 or WO2009/003695.
The thickness of the alkali-ion conducting film (B) can be varied in a wide range. Preferably the alkali-ion conducting film (B) has an average thickness in the range from 0.01 to 1000 μιτι, preferably in the range from 0.01 to 40 μιτι, in particular in the range from 0.05 to 4 μιτι.
In one embodiment of the present invention the alkali-ion conducting separator assembly is characterized in that the alkali-ion conducting film (B) has an average thickness in the range from 0.01 to 40 μιτι, preferably in the range from 0.05 to 4 μιτι.
Preferably the alkali-ion conducting film (B) consists of at least 80% by weight, preferably at least 90% by weight, in particular in the range from 95% to 100% by weight of at least one, preferably one or two, in particular one inorganic material of the general formula (I).
The thickness of the porous membrane (A) and of the alkali-ion conducting film (B) as well as the average diameter of the through pores of the porous membrane (A) can be determined according to Scanning Electron Microscopy (SEM, cross section analysis) or Transmission Electron Microscopy (TEM) measurement.
While the porous membrane (A) itself is permeable to organic solvents the alkali-ion conducting film (B) is impermeable to organic solvents. Therefore the alkali-ion conducting separator assembly is also impermeable to organic solvents.
In one embodiment of the present invention the alkali-ion conducting separator assembly is characterized in that the alkali-ion conducting separator assembly is impermeable to organic solvents.
The present invention further provides a process for producing an alkali-ion conducting separator assembly comprising (A) a porous membrane (A), which consists of at least one inorganic, electrically insulating and non-alkali-ion conducting material, having through pores that extend from one major surface of the membrane to an opposing major surface, and
(B) an alkali-ion conducting film (B) placed on one major surface of the porous membrane (A), wherein the through pores of the porous membrane (A) are sealed by the alkali-ion conducting film (B), wherein the alkali-ion conducting film (B) comprises an inorganic material of the general formula (I)
(L1 +[(12-U)2 + wV]-xm-[(3-y)3+yn]-[(2-z)5+zp] lm+x ) (A3+3-y an+ y) (B5+2-z b + z) (02 2-υ DV" W) (I) in which the variables are each defined as follows:
L is an alkali metal, like Li, Na or K, preferably Li,
I is Mg, Al or Ga, preferably Al,
A is a lanthanide, preferably La,
a is an alkali metal, alkaline earth metal or a lanthanide, preferably Ba,
B is Nb or Ta, preferably Ta,
b is Nb, Ta, Zr, Hf, Ce, Y, W, Mo, Sb, Te, Bi, Sn, Ti or Pr, preferably Zr,
D is F (fluorine), S (sulfur), N (nitrogen) or C (carbon), m is 2 for Mg or 3 for Al or Ga,
n is 1 for alkali metal, 2 for alkaline earth metal or 2, 3 or 4 for lanthanide,
p is 2, 3, 4, 5 or 6 depending on the oxidation state of metal b,
v is 1 for F (fluorine), 2 for S (sulfur), 3 for N (nitrogen) or 4 for C (carbon), w is in the range from 0 to 12, preferably in the range from 0 to 6, in particular 0 to 3, u is in the range from 0 to 12, preferably in the range from 0 to wv/2, in particular wv/2, x is in the range from 0 to 0.75, preferably in the range from 0.25 to 0.35, in particular 0.29, y is in the range from 0 to 3, preferably in the range from 0 to 1 ,
z is in the range from 0 to 2, preferably in the range from 0.5 to 1 .75, comprising the process step of
(a) depositing a layer of a material, which is alkali-ion conducting or which becomes alkali-ion conducting after thermal or chemical, preferably thermal treatment, on one major surface of a porous membrane (A), which consists of inorganic, electrically insulating and non- alkali-ion conducting material, having through pores that extend from one major surface of the membrane to an opposing major surface, and (b) optionally calcination of the porous membrane with the deposited layer formed in process step (a) in a temperature range from 100 °C to 1500 °C, preferably in a temperature range from 500 to 900 °C.
The description and preferred embodiments of the alkali-ion conducting separator assembly and its components, in particular the description of the porous membrane (A) as a first component and of the alkali-ion conducting film (B) as a second component, in the process of the invention correspond to the above description of these components for the alkali-ion conducting separator assembly of the invention.
In process step (a) a layer of a material, which is alkali-ion conducting or which becomes alkali- ion conducting after thermal or chemical, preferably thermal treatment, is deposited on one major surface of a porous membrane (A), which consists of inorganic, electrically insulating and non-alkali-ion conducting material, having through pores that extend from one major surface of the membrane to an opposing major surface.
The layer of the material, which is alkali-ion conducting or which becomes alkali-ion conducting after thermal or chemical, preferably thermal treatment, preferably comprises at least one inorganic material of the general formula (I):
(L1 +[(i2-u)2 + wV]-xm-[(3-y)3+yn] [(2-z)5+zp] lm+x ) (A3+ 3-y an+ y) (B5+ 2-z bP+ z) (02"i2-u Dv w) (I) as described above. The description and preferred embodiments of the variables and the indices of formula (I) correspond to the above description of the inorganic material of formula (I). It is also possible to deposit two or more different inorganic materials of the general formula (I) either together or one after the other on one surface of membrane (A). Preferably the layer of the material consists of at least 80% by weight, preferably at least 90% by weight, in particular in the range from 95% to 100% by weight of at least one, preferably one or two, in particular one inorganic material of the general formula (I).
The person skilled in the art is aware of different methods to deposit inorganic materials in form of a film on a surface of an inorganic target. Preferred deposition methods are pulsed laser deposition (PLD), physical vapor deposition (PVD), chemical vapor deposition (CVD), sputter techniques or (spray) casting methods (spraying/dip coating/sol-gel). A particularly preferred deposition method is pulsed laser deposition (PLD).
In one embodiment of the present invention the inventive process is characterized in that in process step (a) the material, which is alkali-ion conducting or which becomes alkali-ion conducting after thermal or chemical, preferably thermal treatment, is deposited on the surface of the porous membrane (A) by pulsed laser deposition (PLD).
The deposited layer of the material, which is alkali-ion conducting or which becomes alkali-ion conducting after thermal or chemical, preferably thermal treatment, forms a film, that is alkali-ion conducting or becomes alkali-ion conducting after thermal or chemical, in particular thermal treatment, and that seals the through pores of the porous membrane (A) on one major surface of said membrane (A).
In the optional process step (b) the porous membrane with the deposited layer formed in process step (a) is calcined in a temperature range from 100 °C to 1500 °C, preferably in a temperature range from 500 °C to 900 °C. The calcination step can remove possible inhomogenei- ties in the layer of the material which are caused by the deposition method and might convert the deposited material from a non-alkali-ion conducting form to an alkali-ion conducting form. Inhomogeneities can be related to differences in the thickness or to the evenness of the layer or to the chemical or structural composition of the layer. The calcination step might for example also convert the crystal structure of the deposited material.
Alternatively the deposited layer formed in process step (a) can be treated chemically in order to modify the deposited material. Possible methods of chemical treatment of the deposited layer include gas phase reactions (e.g. N2, N H3, NyOx, H2S, H2O, O2, H2, F2, HF, CI2, HCI and combinations of two or more aforementioned gases with defined partial pressures), reaction with molten chemical compounds or molten elements (e.g. (Li/Na)OH, (Li/Na)20, (Li/Na)NC>3 or Li/Na), reaction with evaporated chemical compounds or elements (e.g. U2O, Na20, Li or Na), reaction with in water or organic/ionic liquids dissolved alkali-ion containing (e.g. (Li/Na)OH, (Li/Na)20, (Li/Na)N03, (Li/Na)(B/AI)H4) and/or alkali-ion free compounds (e.g. H202, N2H4, NH3, HN03/ H NO2, H2S, H2SC , H2SO3), plasma treatment (e.g. O2, N2, F or Ar/He and combinations of two or more aforementioned plasmas with defined pressures) and solid-solid reaction either of the deposited layer with the porous membrane (A), of two or more deposited material layers forming (B) or of an additionally deposited layer other than the composition stated in formula (I) with the material of (B) to modify the chemical composition and physico-chemical properties of (B).
The layer deposited in process step (a) and possibly further chemically or thermally treated forms the alkali-ion conducting film (B) of the inventive alkali-ion conducting separator assembly.
The inventive alkali-ion conducting separator assemblies are particularly suitable as separator or as constituent of a separator in electrochemical cells, in particular in rechargeable electrochemical cells.
For the purposes of the present invention, the term electrochemical cell or battery encompasses batteries, capacitors and accumulators (secondary batteries) of any type, in particular alkali metal cells or batteries such as lithium, lithium ion, lithium-sulfur, alkali metal-oxygen and alkaline earth metal batteries and accumulators, including in the form of high-energy or high-power systems, and also electrolyte capacitors and double-layer capacitors which are known under the names Supercaps, Goldcaps, BoostCaps or Ultracaps. The present invention further provides a rechargeable electrochemical cell comprising at least one alkali-ion conducting separator assembly as described above.
The alkali-ion conducting separator assemblies of the invention are preferably suitable for electrochemical cells which are based on the transfer of alkali metal ions, in particular for lithium metal, lithium-sulfur, alkali metal-oxygen and lithium ion cells or batteries and especially for lithium ion secondary cells or secondary batteries. The alkali-ion conducting separator assemblies of the invention are particularly suitable for rechargeable electrochemical cells from the group of lithium-sulfur cells and alkali metal-oxygen cells.
The present invention further provides a rechargeable electrochemical cell comprising
(a) at least one cathode (a),
(b) at least one anode, preferably comprising at least one alkali metal,
(c) at least one electrolyte composition (c) comprising (c1 ) at least one aprotic organic solvent (c1 ), and (c2) at least one alkali metal salt (c2), and
(d) at least one alkali-ion conducting separator assembly as described above.
As regards suitable cathode materials, suitable anode materials, suitable electrolytes and possible arrangements, reference is made to the relevant prior art, e.g. appropriate monographs and reference works: e.g. Wakihara et al. (editor): Lithium ion Batteries, 1st edition, Wiley VCH, Weinheim, 1998; David Linden: Handbook of Batteries (McGraw-Hill Handbooks), 3rd edition, Mcgraw-Hill Professional, New York 2008; J. O. Besenhard: Handbook of Battery Materials. Wiley-VCH, 1998.
In the context with the present invention, the electrode where during discharging a net positive charge occurs is called the cathode.
The inventive rechargeable electrochemical cell comprises at least one cathode (a). Possible cathodes are, in particular, cathodes in which the cathode material comprises a lithium- transition metal oxide, e.g. lithium-cobalt oxide, lithium-nickel oxide, lithium-cobalt-nickel oxide, lithium-manganese oxide (spinel), lithium-nickel-cobalt-aluminum oxide, lithium-nickel-cobalt- manganese oxide or lithium-vanadium oxide, a lithium sulfide or lithium polysulfide such as U2S, L12S8, L12S6, L12S4 or L12S3 or a lithium-transition metal phosphate such as lithium-iron phosphate as electroactive constituent. Cathode materials which comprise iodine, oxygen, sulfur and the like as electroactive constituent are also suitable. However, if materials comprising sulfur or po- lymers comprising polysulfide bridges are to be used as cathode materials, it has to be ensured that the anode is charged with Li° before such an electrochemical cell can be discharged and recharged. For this purpose lithium can be directly deposited (e.g. vapor deposition preferably sputtering, thermal vapor deposition or pulsed laser deposition, in particular thermal vapor deposition) on the open surface of the alkali-ion conducting film (B), which is placed with its opposite surface on the porous membrane (A). Gas diffusion electrodes, which are permeable to oxidizing gases, in particular to molecular oxygen O2, are known and used as cathodes in alkali metal-oxygen cells. The alkali-ion conducting separator assembly is preferably used in inventive rechargeable electrochemical cells, wherein the at least one cathode (a) comprises an electro- active chalcogen-containing material, preferably an oxygen- or sulfur-containing material, in particular elemental sulfur.
In one embodiment of the present invention the inventive rechargeable electrochemical cell is characterized in that the at least one cathode (a) comprises an electroactive chalcogen- containing material, preferably an oxygen- or sulfur-containing material, in particular elemental sulfur.
Cathode (a) may comprise one or further constituents. For example, cathode (a) may comprise carbon in an electrical conductive polymorph, for example selected from graphite, carbon black, carbon nanotubes, graphene or mixtures of at least two of the aforementioned substances.
In addition, cathode (a) may comprise one or more binders, for example one or more organic polymers. Suitable binders may be selected, for example, from those binders which are described in WO 201 1/161598, page 6, line 28 to page 8, line 15, where the binder is referred to as polymer (C) or binder (C).
Particularly suitable binders for the cathode (a) are especially polyvinyl alcohol and halogenated (co)polymers, for example polyvinyl chloride or polyvinylidene chloride, especially fluorinated (co)polymers such as polyvinyl fluoride and especially polyvinylidene fluoride and
polytetrafluoroethylene.
In addition, cathode (a) may have further constituents customary per se, for example an output conductor, which may be configured in the form of a metal wire, metal grid, metal mesh, expanded metal, metal sheet or metal foil. Suitable metal foils are especially aluminum foils.
In one embodiment of the present invention, cathode (a) has a thickness in the range from 25 to 200 μιτι, preferably from 30 to 100 μιτι, based on the thickness without output conductor.
The inventive rechargeable electrochemical cell further comprises, as well as the inventive alkali-ion conducting separator assembly and the cathode (a), at least one anode (b). In the context with the present invention, the electrode where during discharging a net negative charge occurs is called the anode.
In an embodiment of the present invention, anode (b) can be selected from among anodes composed of carbon, anodes comprising Sn or Si, anodes comprising lithium titanate of the formula Li4+xTisOi2 in which x is a numerical value from > 0 to 3, and anodes comprising an alkali metal, preferably lithium or sodium, in particular lithium. Anodes composed of carbon can, for example, be selected from among hard carbon, soft carbon, graphene, graphite and in particular graphite, intercalated graphite and mixtures of two or more of the abovementioned carbons. Anodes comprising Sn or Si can, for example be selected from among nanoparticulate Si or Sn powder, Si or Sn fibers, carbon-Si or carbon-Sn composites and Si-metal or Sn-metal alloys. The alkali metal, preferably lithium or sodium, in particular lithium, may be present in the form of pure alkali metal or in the form of an alloy of an alkali metal with at least another metal or in the form of an alkali metal carbon intercalation compound. The alkali-ion conducting separator assembly is preferably used in inventive rechargeable electrochemical cells, wherein the at least one anode (b) comprises an alkali metal, preferably lithium or sodium, in particular lithium.
In one embodiment of the present invention the inventive rechargeable electrochemical cell is characterized in that the at least one anode (b) comprises an alkali metal, preferably lithium or sodium, in particular lithium. As described above it is possible to deposit lithium directly to the open surface of the alkali-ion conducting film (B) of the separator assembly for example by vapor deposition or similar techniques, in particular thermal vapor deposition or pulsed laser deposition, preferably thermal vapor deposition.
Apart from the electroactive constituents the anode (b) can also comprise further constituents, for example
electrically conductive or electroactive constituents such as carbon black, graphite, carbon fibers, carbon nanofibers, carbon nanotubes or electrically conductive polymers;
binders such as polyethylene oxide (PEO), cellulose, carboxymethylcellulose (CMC), polyethylene, polypropylene, polytetrafluoroethylene, polyacrylonitrile-methyl methacrylate, polyvinyl alcohol, polytetrafluoroethylene, styrene-butadiene copolymers, tetrafluoroeth- ylene-hexafluoroethylene copolymers, polyvinylidene difluoride (PVdF), polyvinylidene difluoride-hexafluoropropylene copolymers (PVdF-HFP), tetrafluoroethylene-hexa- fluoropropylene copolymers, tetrafluoroethylene, perfluoroalkyl-vinyl ether copolymers, vinylidene fluoride-hexafluoropropylene copolymers, ethylene-tetrafluoroethylene copolymers, vinylidene fluoride-chlorotrifluoroethylene copolymers, ethylene-chloro- fluoroethylene copolymers, ethylene-acrylic acid copolymers (with and without inclusion of lithium/sodium ions), ethylene-methacrylic acid copolymers (with and without inclusion of lithium/sodium ions), ethylene-methacrylic ester copolymers (with and without inclusion of lithium/sodium ions), polyimides and polyisobutene. In addition, anode (b) may have further constituents customary per se, for example an output conductor which may be configured in the form of a metal wire, metal grid, metal mesh, expanded metal, or a metal foil or metal sheet. Suitable metal foils are especially copper foils.
In one embodiment of the present invention, anode (b) has a thickness in the range from 15 to 200 μιτι, preferably from 30 to 100 μιτι, based on the thickness without output conductor.
The inventive rechargeable electrochemical cell further comprises, as well as the inventive alkali-ion conducting separator assembly, the cathode (a) and the anode (b), at least one electrolyte composition (c) comprising
(c1 ) at least one aprotic organic solvent (c1 ), and
(c2) at least one alkali metal salt (c2).
Possible aprotic organic solvents (c1 ) may be liquid or solid at room temperature and are preferably liquid at room temperature. Solvents (c1 ) are preferably selected from polymers, cyclic or noncyclic ethers, cyclic or noncyclic acetals, cyclic or noncyclic organic carbonates and ionic liquids.
In one embodiment of the present invention the inventive rechargeable electrochemical cell is characterized in that the aprotic organic solvent (c1 ) is selected from polymers, cyclic or noncyclic ethers, noncyclic or cyclic acetals and cyclic or noncyclic organic carbonates.
Examples of suitable polymers are especially polyalkylene glycols, preferably poly-Ci-C4- alkylene glycols and especially polyethylene glycols. Polyethylene glycols may comprise up to 20 mol% of one or more Ci-C4-alkylene glycols in copolymerized form. Polyalkylene glycols are preferably doubly methyl- or ethyl-capped polyalkylene glycols.
The molecular weight Mw of suitable polyalkylene glycols and especially of suitable polyethylene glycols may be at least 400 g/mol.
The molecular weight Mw of suitable polyalkylene glycols and especially of suitable polyethylene glycols may be up to 5 000 000 g/mol, preferably up to 2 000 000 g/mol.
Examples of suitable noncyclic ethers are, for example, diisopropyl ether, di-n-butyl ether, 1 ,2- dimethoxyethane, 1 ,2-diethoxyethane, preference being given to 1 ,2-dimethoxyethane.
Examples of suitable cyclic ethers are tetrahydrofuran and 1 ,4-dioxane.
Examples of suitable noncyclic acetals are, for example, dimethoxymethane, diethoxymethane, 1 ,1 -dimethoxyethane and 1 ,1 -diethoxyethane.
Examples of suitable cyclic acetals are 1 ,3-dioxane and especially 1 ,3-dioxolane. Examples of suitable noncyclic organic carbonates are dimethyl carbonate, ethyl methyl carbonate and diethyl carbonate.
Examples of suitable cyclic organic carbonates are compounds of the general formulae (X) and (XI)
Figure imgf000014_0001
in which R1, R2 and R3 may be the same or different and are each selected from hydrogen and Ci-C4-alkyl, for example methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl and tert- butyl, where R2 and R3 are preferably not both tert-butyl.
In particularly preferred embodiments, R1 is methyl and R2 and R3 are each hydrogen, or R1, R2 and R3 are each hydrogen.
Another preferred cyclic organic carbonate is vinylene carbonate, formula (XII).
O
o X o
\^/ (xii)
Preference is given to using the solvent(s) in what is called the anhydrous state, i.e. with a water content in the range from 1 ppm to 0.1 % by weight, determinable, for example, by Karl Fischer titration.
Possible alkali metal salts (c2), which are used as conductive salts, have to be soluble in the aprotic organic solvent (c1 ). Preferred alkali metal salts (c2) are lithium salts or sodium salts, in particular lithium salts.
In one embodiment of the present invention the inventive rechargeable electrochemical cell is characterized in that wherein the alkali metal salt (c2) is a lithium salt or sodium salt, preferably a lithium salt. Suitable alkali metal salts are especially lithium salts. Examples of suitable lithium salts are
LiPF6, LiBF4, L1CIO4, LiAsFe, UCF3SO3, LiC(CnF2n+iS02)3, lithium imides such as
LiN(CnF2n+iSC>2)2, where n is an integer in the range from 1 to 20, LiN(SC>2F)2, Li2SiF6, LiSbF6,
LiAICU, and salts of the general formula (CnF2n+iS02)mXLi, where m is defined as follows:
m = 1 when X is selected from oxygen and sulfur,
m = 2 when X is selected from nitrogen and phosphorus, and
m = 3 when X is selected from carbon and silicon.
Preferred alkali metal salts are selected from LiC(CF3S02)3, LiN(CF3S02)2, LiPF6, LiBF4, L1CIO4, and particular preference is given to LiPF6 and LiN(CF3SC>2)2.
The through pores of the porous membrane (A), which are open on the major side opposite to the sealing alkali-ion conducting film (B) can be filled either with suitable cathode materials, suitable anode materials or suitable electrolytes. Preferably the pores of the porous membrane (A) are filled with electrolyte composition (c) as described above.
In one embodiment of the present invention the inventive rechargeable electrochemical cell is characterized in that the alkali-ion conducting separator assembly comprises one porous, inorganic, non-alkali-ion conducting membrane (A) having through pores that extend from one major surface of the membrane to an opposing major surface, wherein an alkali-ion conducting film (B) is placed on one major surface of the porous, inorganic, non-alkali-ion conducting membrane (A) and the porous membrane (A) is filled with electrolyte composition (c).
Inventive rechargeable electrochemical cells further comprise a housing which may be of any shape, for example cuboidal or in the shape of a cylinder. In another embodiment, inventive rechargeable electrochemical cells have the shape of a prism. In one variant, the housing used is a metal-plastic composite film processed as a pouch.
The inventive rechargeable electrochemical cells can be assembled to rechargeable batteries, preferably rechargeable alkali metal ion batteries like lithium ion batteries, lithium sulfur batteries, lithium air batteries or sodium air batteries, in particular lithium sulfur batteries.
Accordingly, the present invention also further provides for the use of inventive rechargeable electrochemical cells as described above in rechargeable batteries, especially rechargeable lithium sulfur batteries.
The present invention further provides an alkali metal ion battery comprising at least one rechargeable electrochemical cell as described above. Inventive rechargeable electrochemical cells can be combined with one another in inventive alkali metal ion batteries, for example in series connection or in parallel connection. Series connection is preferred. Inventive rechargeable electrochemical cells are notable for particularly high capacities, high performances even after repeated charging and greatly retarded cell death. Inventive rechargeable electrochemical cells are very suitable for use in motor vehicles, bicycles operated by electric motor (e.g. pedelecs), aircraft, ships and boats or stationary energy storage. Such uses form a further part of the subject matter of the present invention.
The present invention further provides for the use of inventive rechargeable electrochemical cells as described above in motor vehicles, bicycles operated by electric motor, aircraft, ships and boats or stationary energy storage.
The use of inventive rechargeable electrochemical cells in devices gives the advantage of prolonged run time before recharging and a smaller loss of capacity in the course of prolonged run time. If the intention were to achieve an equal run time with electrochemical cells with lower energy density, a higher weight for electrochemical cells would have to be accepted.
The present invention therefore further provides for the use of inventive rechargeable electrochemical cells in devices, especially in mobile devices. Examples of mobile devices are vehicles, for example automobiles, bicycles, aircraft, or water vehicles such as boats or ships. Other examples of mobile devices are those which are portable, for example computers, especially laptops, telephones or electrical power tools, for example from the construction sector, especially drills, battery-driven screwdrivers or battery-driven tackers.
The present invention further provides a device comprising at least one rechargeable electrochemical cell as described above.
The invention is illustrated by the examples which follow but do not restrict the invention.
Figures in percent are each based on % by weight, unless explicitly stated otherwise.
Li6BaLa2Ta20i2 as target material for pulsed laser deposition (PLD) was prepared by solid state reaction according to J. Awaka, N. Kijima, H. Hayakawa and J. Akimoto, Journal of Solid State Chemistry, 2009, 182, 2046.
I. Preparation of alkali-ion conducting separator assemblies by depositing a film of
Li6BaLa2Ta20i2 on anodized aluminum oxide (AAO) membrane
The deposition of lithium ion conducting garnet-type material on top of porous AAO was carried out by pulsed laser deposition (PLD). The PLD (Surface GmbH & Co. KG, Frankfurt am Main, Germany) was directly attached to an argon gas filled glove box (M. Braun GmbH, Garching, Germany) to avoid air contact of the samples. Li6BaLa2Ta20i2 was used as target. An AAO disc (Anopore™ inorganic membrane (Anodisc™) by Whatman pic, Maidstone, Kent, UK) with a diameter of 13 mm, average pore size of 100 nm and thickness of 60 μιτι was used as a sub- strate. A KrF Excimer Laser (Compex 201 F, Coherent Inc., Santa Clara, CA, USA) with a wavelength of 248 nm was used for the deposition of the garnet-type thin films. Prior to ablation the PLD chamber was evacuated to 1 x10-5 mbar. The deposition process took place in pure 5x10-2 mbar oxygen atmosphere (higher and lower pressure values were also possible, e.g. deposition at 2x10"2 mbar oxygen atmosphere was also possible). The distance between target and substrate was set to 45 mm. It turned out, that this parameter (distance), which could be adjusted from 40 mm - 85 mm, had little to no influence on the crystal structure of the deposited material but that it had a bigger influence on the deposition rate and film morphology. The substrate was attached to a metallic substrate holder by a mask with a hole of 12 mm and the substrate holder was heated to 840 °C by an IR-laser heater. However, this temperature is the temperature measured at the backside of the substrate holder with a Pyrometer and was not the surface temperature of the substrate. The surface temperature of the substrate was believed to be in the range from 500 °C - 800 °C. The type of heater, IR-Laser or any other type of heat source is not relevant. The laser fluence was adjusted in the range from 2 J/cm2 to 4 J/cm2. The laser frequency was adjusted to 10 Hz wherein the laser frequency has an influence on the deposition rate. The thin films had thicknesses between 0.5 μιτι and 3 μιτι.
1.1 Alkali-ion conducting separator assembly SA.1
SA.1 was prepared as described in example I. with following parameters:
Substrate: AAO-disk from Whatman; diameter: 13 mm; pore sizes: 100 nm; thickness: 60 μιτι.
Target: Chemical composition: Li6BaLa2Ta20i2 (ICP-OES, EDS for Ba, La and Ta)
Electrical conductivity: 6 - 7x10-7 S/cm (electrochemical impedance spectroscopy)
SA.1 : Thickness of alkali-ion conducting film (B): 1 μιτι (SEM, cross-section)
Diameter of alkali-ion conducting film (B): 12 mm (defined by mask)
Morphology: dense and visually homogeneous (SEM, top-view) thin film Porosity: visually (SEM, cross-section and top-view) no open porosity
Crystal structure: cubic garnet-type phase (XRD, preferred orientation)
Figure 1 shows a SEM cross-section of SA.1 (LBLTO on AAO)
I.2 Alkali-ion conducting separator assembly SA.2
Experiment I. was repeated, except that Li6.5La3Zr1.5Tao.5O12 was used as target in place of Li6BaLa2Ta20i2 to produce alkali-ion conducting separator assembly SA.2. Li6.5La3Zr1.5Tao.5O12 was prepared according to J. Power Sources 2012, 236-244.
Substrate: AAO-disk from Whatman; diameter: 13 mm; pore sizes: 100 nm; thickness: 60 μιτι. Target: Chemical composition: Li6.5La3Zr1.5Tao.5O12
II. Electrochemical testing of alkali-ion conducting separator assemblies Cathode (a)
For the preparation of the cathodes (a) sulfur, conductive carbon additives (Printex XE2 (Orion) and Super C65 (TIMCAL™) in a ratio of 1 :1 ) and polyvinyl alcohol) (Aldrich) were mixed with mass ratio of 60:35:5 in water to form a slurry. The slurry was then coated onto aluminum foil (20 μιτι) with a doctor's blade and dried in vacuum at 40 °C for 16 h.
Anode (b)
Lithium foil (China Lithium Ltd., 600 μιτι, 8 mm) Electrolyte (c)
The electrolyte was a solution of 12 wt% lithium bis(trifluromethanesulfonyl)imide (LiTFSI) (Aldrich, 99.95%), 44 wt% of 1 ,2-dimethoxyethane (DME) (Alfa Aesar, 99+%) and 44 wt% 1 ,3- dioxolane (DOL) (Acros, 99.8%). The electrolyte solvents were purified by distillation from sodium potassium alloy under argon atmosphere.
11.1 Production of an inventive electrochemical cell EC.1 and testing
A coin-type cell was assembled in an argon-filled glovebox using a sulfur cathode (a) with an electrode diameter of 8 mm, the alkali-ion conducting separator assembly SA.1 produced according to 1.1 (diameter of (A) 13 mm and (B) 12 mm, respectively) and lithium foil (China Lithium Ltd., 600 μιτι, 8 mm) as negative electrode (anode (b)). Additionally a glass fiber separator (GF/A, Whatman) was placed between anode (b) and the Li-ion conductive film (B). The cathode electrode (a) was assembled on the opposite side of the Li-ion conductive film (B) and directly on the porous membrane (A). The glass fiber separator (C) and positive electrode (a) were soaked with electrolyte (c).
Discharge-charge cycling of the cell was performed at 0.036 mA (corresponds to a rate of C/50 for the used cathode electrode) for the first cycle with a discharge cutoff voltage of 1.7 V and charge cutoff at 2.5 V. For the subsequent cycles a discharge current of 0.36 mA, and charge current of 0.22 mA was applied. This corresponds to a discharge rate of C/5 and a charge rate of C/8 for this cell. The electrochemical experiments were carried out under controlled and constant environmental conditions.
Figure 2 shows the schematic structure of the different layers of the electrochemical cell EC.1. The annotations in Figure 2 mean:
(A) porous membrane (A)
(B) Li-ion conductive film (B)
(C) glass fiber separator (C)
(D) anode (b)
(E) cathode (a)
Figure 3 shows the voltage profile of the Li/S cell EC.1. Plotted are the first cycle with an applied current of 0.036 mA for charge and discharge, and the second cycle with a discharged current of 0.36 mA and charge current of 0.22 mA.
Figure 4 shows the electrochemical performance of the Li/S cell EC.1 .
11.2 Production of an inventive electrochemical cell EC.2
A coin-type cell was assembled in an argon-filled glovebox using a sulfur cathode (a) with an electrode diameter of 8 mm and the alkali-ion conducting separator assembly SA.1 produced according to 1.1 (diameter of (A) 13 mm and (B) 12 mm, respectively), wherein a layer of lithium
(F) has been deposited directly on the Li-ion conductive film (B) of the separator assembly SA.1 by thermal vapor deposition. The positive electrode (sulfur cathode (a)) was soaked with electrolyte while the compartment of the lithium deposited (F) membrane (A)+(B) contains no electrolyte.
Figure 5 shows the schematic structure of the different layers of the electrochemical cell EC.2. The annotations in Figure 5 mean:
(A) porous membrane (A)
(B) Li-ion conductive film (B)
(F) anode (b)
(E) cathode (a)

Claims

Claims
1 . An alkali-ion conducting separator assembly comprising
(A) a porous membrane (A), which consists of at least one inorganic, electrically insulating and non-alkali-ion conducting material, having through pores that extend from one major surface of the membrane to an opposing major surface, and
(B) an alkali-ion conducting film (B) placed on one major surface of the porous membrane (A), wherein the through pores of the porous membrane (A) are sealed by the alkali-ion conducting film (B), wherein the alkali-ion conducting film (B) comprises an inorganic material of the general formula (I)
(L1 +[(12-U)2 + wV]-xm-[(3-y)3+yn]-[(2-z)5+zp] lm+x ) (A3+3-y an+ y) (B5+2-z b + z) (02 2-υ DV" W) (I) in which the variables are each defined as follows:
L is an alkali metal,
I is Mg, Al or Ga,
A is a lanthanide,
a is an alkali metal, alkaline earth metal or a lanthanide,
B is Nb or Ta,
b is Nb, Ta, Zr, Hf, Ce, Y, W, Mo, Sb, Te, Bi, Sn, Ti or Pr,
D is F (fluorine), S (sulfur), N (nitrogen) or C (carbon), m is 2 for Mg or 3 for Al or Ga,
n is 1 for alkali metal, 2 for alkaline earth metal or 2, 3 or 4 for lanthanide,
p is 2, 3, 4, 5 or 6 depending on the oxidation state of metal b,
v is 1 for F (fluorine), 2 for S (sulfur), 3 for N (nitrogen) or 4 for C (carbon), w is in the range from 0 to 12,
u is in the range from 0 to 12,
X is in the range from 0 to 0.75,
y is in the range from 0 to 3,
z is in the range from 0 to 2.
2. The alkali-ion conducting separator assembly according to claim 1 , wherein the inorganic, electrically insulating and non-alkali-ion conducting material of porous membrane (A) is selected from the group consisting of ceramics, sintered ceramics, glass-ceramics and glasses.
3. The alkali-ion conducting separator assembly according to claim 1 or 2, wherein the porous membrane (A) has an average thickness in the range from 5 to 500 μιτι.
4. The alkali-ion conducting separator assembly according to any of claims 1 to 3, wherein the alkali-ion conducting film (B) has an average thickness in the range from 0.01 to 40 μιτι.
5. The alkali-ion conducting separator assembly according to any of claims 1 to 4, wherein the alkali-ion conducting separator assembly is impermeable to organic solvents.
6. A process for producing an alkali-ion conducting separator assembly according to any of claims 1 to 5, comprising the process step of
(a) depositing a layer of a material, which is alkali-ion conducting or which becomes alkali-ion conducting after thermal or chemical treatment, on one major surface of a porous membrane (A), which consists of inorganic, electrically insulating and non- alkali-ion conducting material, having through pores that extend from one major surface of the membrane to an opposing major surface, and
(b) optionally calcination of the porous membrane with the deposited layer formed in process step (a) in a temperature range from 100 °C to 1500 °C.
7. A rechargeable electrochemical cell comprising
(a) at least one cathode (a),
(b) at least one anode (b),
(c) at least one electrolyte composition (c) comprising (c1 ) at least one aprotic organic solvent (c1 ), and (c2) at least one alkali metal salt (c2), and
(d) at least one alkali-ion conducting separator assembly according to any of claims 1 to 5.
8. The rechargeable electrochemical cell according to claim 7, wherein the at least one cathode (a) comprises an electroactive chalcogen-containing material.
9. The rechargeable electrochemical cell according to claim 7 or 8, wherein the at least one anode (b) comprises an alkali metal.
10. The rechargeable electrochemical cell according to any of claims 7 to 9, wherein the apro- tic organic solvent (c1 ) is selected from polymers, cyclic or noncyclic ethers, noncyclic or cyclic acetals and cyclic or noncyclic organic carbonates.
1 1 . The rechargeable electrochemical cell according to any of claims 7 to 10, wherein the alkali metal salt (c2) is a lithium salt or sodium salt.
12. The rechargeable electrochemical cell according to any of claims 7 to 1 1 , wherein the alkali-ion conducting separator assembly comprises one porous, inorganic, non-alkali-ion conducting membrane (A) having through pores that extend from one major surface of the membrane to an opposing major surface, wherein an alkali-ion conducting film (B) is placed on one major surface of the porous, inorganic, non-alkali-ion conducting membrane (A) and the porous membrane (A) is filled with electrolyte composition (c).
13. Alkali metal ion battery comprising at least one rechargeable electrochemical cell according to any of claims 7 to 12.
14. A device comprising at least one rechargeable electrochemical cell according to any of claims 7 to 12.
PCT/IB2014/061752 2013-06-19 2014-05-27 Alkali-ion conductive separator assembly for rechargeable electrochemical cells WO2014203100A2 (en)

Priority Applications (5)

Application Number Priority Date Filing Date Title
CN201480034089.1A CN105409051A (en) 2013-06-19 2014-05-27 Alkali-ion conductive separator assembly for rechargeable electrochemical cells
US14/899,899 US20160141580A1 (en) 2013-06-19 2014-05-27 Alkali-ion conductive separator assembly for rechargeable electrochemical cells
JP2016520768A JP2016526757A (en) 2013-06-19 2014-05-27 Alkaline ion conductive separator assembly for rechargeable electrochemical cells
EP14814477.7A EP3011629A4 (en) 2013-06-19 2014-05-27 Alkali-ion conductive separator assembly for rechargeable electrochemical cells
KR1020167001310A KR20160021841A (en) 2013-06-19 2014-05-27 Alkali-ion conductive seperator assembly for rechargeable electrochemical cells

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
EP13172768 2013-06-19
EP13172768.7 2013-06-19

Publications (2)

Publication Number Publication Date
WO2014203100A2 true WO2014203100A2 (en) 2014-12-24
WO2014203100A3 WO2014203100A3 (en) 2015-02-19

Family

ID=48628481

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/IB2014/061752 WO2014203100A2 (en) 2013-06-19 2014-05-27 Alkali-ion conductive separator assembly for rechargeable electrochemical cells

Country Status (6)

Country Link
US (1) US20160141580A1 (en)
EP (1) EP3011629A4 (en)
JP (1) JP2016526757A (en)
KR (1) KR20160021841A (en)
CN (1) CN105409051A (en)
WO (1) WO2014203100A2 (en)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP3116052A1 (en) 2015-07-08 2017-01-11 Basf Se Rechargeable metal-oxygen cells

Families Citing this family (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US11888149B2 (en) 2013-03-21 2024-01-30 University Of Maryland Solid state battery system usable at high temperatures and methods of use and manufacture thereof
US10693183B2 (en) * 2015-04-09 2020-06-23 Battelle Memorial Institute Ether-based electrolyte for Na-ion battery anode
US9966630B2 (en) * 2016-01-27 2018-05-08 Quantumscape Corporation Annealed garnet electrolyte separators
KR102457505B1 (en) * 2016-06-21 2022-10-20 시온 파워 코퍼레이션 Coatings for parts of electrochemical cells
US20200112050A1 (en) * 2017-03-29 2020-04-09 University Of Maryland, College Park Solid-state hybrid electrolytes, methods of making same, and uses thereof
US11081726B2 (en) 2018-01-30 2021-08-03 Industrial Technology Research Institute Solid state electrolyte and solid state battery
KR20200121827A (en) 2018-02-15 2020-10-26 유니버시티 오브 매릴랜드, 칼리지 파크 Aligned porous solid electrolyte structure, electrochemical device including same, and method of manufacturing same
JP7104148B2 (en) * 2018-05-17 2022-07-20 日本碍子株式会社 Lithium secondary battery
US11444318B2 (en) * 2019-01-11 2022-09-13 Samsung Electronics Co., Ltd. Garnet-type lithium-ion solid-state conductor
KR20210102738A (en) * 2020-02-12 2021-08-20 삼성전자주식회사 Composite solid electrolyte, preparaing method thereof, and electrochemical battery including the composite solid electrolyte
US11721834B2 (en) * 2020-07-29 2023-08-08 Samsung Electronics Co., Ltd. Solid-state electrolyte, solid-state battery including the electrolyte, and method of making the same
KR102434870B1 (en) 2020-08-19 2022-08-22 엘에스일렉트릭(주) Module install apparatus and modular multilevel converter include the same

Family Cites Families (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP4848582B2 (en) * 2000-10-06 2011-12-28 ソニー株式会社 Method for producing positive electrode active material
US20110223487A1 (en) * 2007-08-29 2011-09-15 Excellatron Solid State Llc Electrochemical cell with sintered cathode and both solid and liquid electrolyte
US8323817B2 (en) * 2008-09-12 2012-12-04 Ceramatec, Inc. Alkali metal seawater battery
JP5525388B2 (en) * 2009-09-03 2014-06-18 日本碍子株式会社 Ceramic material and manufacturing method thereof
JP5381640B2 (en) * 2009-11-24 2014-01-08 株式会社豊田中央研究所 Lithium secondary battery
JP5471527B2 (en) * 2010-02-02 2014-04-16 株式会社豊田中央研究所 Lithium secondary battery and electrode for lithium secondary battery
US8828575B2 (en) * 2011-11-15 2014-09-09 PolyPlus Batter Company Aqueous electrolyte lithium sulfur batteries

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP3116052A1 (en) 2015-07-08 2017-01-11 Basf Se Rechargeable metal-oxygen cells

Also Published As

Publication number Publication date
JP2016526757A (en) 2016-09-05
EP3011629A4 (en) 2016-11-09
WO2014203100A3 (en) 2015-02-19
KR20160021841A (en) 2016-02-26
US20160141580A1 (en) 2016-05-19
EP3011629A2 (en) 2016-04-27
CN105409051A (en) 2016-03-16

Similar Documents

Publication Publication Date Title
US20160141580A1 (en) Alkali-ion conductive separator assembly for rechargeable electrochemical cells
KR100508945B1 (en) Negative electrode for lithium battery, method of preparing same, and lithium battery comprising same
US9502735B1 (en) Fabrication methods to produce lithium battery structures with composite layers
Kim et al. Metallic anodes for next generation secondary batteries
JP2024026161A (en) Ionically conductive compounds and related uses
KR101981609B1 (en) Negative electrode active material for lithium secondary battery and method of preparing for the same
JP5614307B2 (en) Nonaqueous electrolyte secondary battery
WO2016012275A1 (en) Composites comprising mxenes for cathodes of lithium sulfur cells
JP2004146292A (en) Non-aqueous electrolyte secondary battery
KR20150112746A (en) Negative active material for lithium secondary battery and method of preparing for the same
JPWO2018123322A1 (en) Negative electrode active material, negative electrode, battery, battery pack, electronic device, electric vehicle, power storage device, and power system
KR20200044231A (en) Negative electrode for lithium secondary battery, lithium secondary batter comprsing the same, and methoe for preparing thereof
JP5343516B2 (en) Negative electrode for lithium secondary battery, lithium secondary battery, and method for producing negative electrode for lithium secondary battery
WO2015110333A1 (en) Electrochemical cells comprising alkali-ion conducting composite membranes
CN113597696A (en) Negative electrode sheet, electrochemical device, and electronic device
JP2005026230A (en) Negative electrode for lithium secondary battery, its manufacturing method and the battery including the electrode
KR20140048821A (en) Manufacturing method of silicon oxide
KR20190042992A (en) Lithium Secondary Battery
WO2015185400A1 (en) Metal oxide coated cathodes comprising sulfur for electrochemical cells
WO2015165762A1 (en) Process for producing a monolithic body of a porous carbon material, monolithic bodies of special porous carbon materials and their use
KR20190066867A (en) Negative electrode active material, negative electrode including the negative electrode active material, and lithium secondary battery including the same
KR102593273B1 (en) Lithium secondary battery
WO2015086759A1 (en) Alkali-ion conducting composite membranes for electronic applications
WO2022208978A1 (en) Lithium ion secondary battery
CN110998928B (en) Negative electrode active material and method for producing same

Legal Events

Date Code Title Description
WWE Wipo information: entry into national phase

Ref document number: 201480034089.1

Country of ref document: CN

REEP Request for entry into the european phase

Ref document number: 2014814477

Country of ref document: EP

WWE Wipo information: entry into national phase

Ref document number: 2014814477

Country of ref document: EP

WWE Wipo information: entry into national phase

Ref document number: 14899899

Country of ref document: US

ENP Entry into the national phase

Ref document number: 2016520768

Country of ref document: JP

Kind code of ref document: A

ENP Entry into the national phase

Ref document number: 20167001310

Country of ref document: KR

Kind code of ref document: A

121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 14814477

Country of ref document: EP

Kind code of ref document: A2