[go: up one dir, main page]

WO2017017944A1 - Composés d'oxydes de métaux de transition à base de sodium pour batteries na-ion - Google Patents

Composés d'oxydes de métaux de transition à base de sodium pour batteries na-ion Download PDF

Info

Publication number
WO2017017944A1
WO2017017944A1 PCT/JP2016/003436 JP2016003436W WO2017017944A1 WO 2017017944 A1 WO2017017944 A1 WO 2017017944A1 JP 2016003436 W JP2016003436 W JP 2016003436W WO 2017017944 A1 WO2017017944 A1 WO 2017017944A1
Authority
WO
WIPO (PCT)
Prior art keywords
sodium
oxidation state
capacity
composition according
transition metal
Prior art date
Legal status (The legal status 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 status listed.)
Ceased
Application number
PCT/JP2016/003436
Other languages
English (en)
Inventor
Emma Kendrick
Robert Gruar
Katherine Louise Smith
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Sharp Corp
Original Assignee
Sharp Corp
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 Sharp Corp filed Critical Sharp Corp
Publication of WO2017017944A1 publication Critical patent/WO2017017944A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

Links

Images

Classifications

    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G53/00—Compounds of nickel
    • C01G53/40—Complex oxides containing nickel and at least one other metal element
    • C01G53/42—Complex oxides containing nickel and at least one other metal element containing alkali metals, e.g. LiNiO2
    • C01G53/44—Complex oxides containing nickel and at least one other metal element containing alkali metals, e.g. LiNiO2 containing manganese
    • C01G53/50—Complex oxides containing nickel and at least one other metal element containing alkali metals, e.g. LiNiO2 containing manganese of the type (MnO2)n-, e.g. Li(NixMn1-x)O2 or Li(MyNixMn1-x-y)O2
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G53/00—Compounds of nickel
    • C01G53/40—Complex oxides containing nickel and at least one other metal element
    • C01G53/42—Complex oxides containing nickel and at least one other metal element containing alkali metals, e.g. LiNiO2
    • C01G53/44—Complex oxides containing nickel and at least one other metal element containing alkali metals, e.g. LiNiO2 containing manganese
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G23/00—Compounds of titanium
    • C01G23/003—Titanates
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G45/00—Compounds of manganese
    • C01G45/12—Complex oxides containing manganese and at least one other metal element
    • C01G45/1221—Manganates or manganites with trivalent manganese, tetravalent manganese or mixtures thereof
    • C01G45/1228—Manganates or manganites with trivalent manganese, tetravalent manganese or mixtures thereof of the type (MnO2)-, e.g. LiMnO2 or Li(MxMn1-x)O2
    • 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
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/131—Electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/485—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of mixed oxides or hydroxides for inserting or intercalating light metals, e.g. LiTi2O4 or LiTi2OxFy
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/50—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese
    • H01M4/505—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese of mixed oxides or hydroxides containing manganese for inserting or intercalating light metals, e.g. LiMn2O4 or LiMn2OxFy
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/52—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
    • H01M4/525—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron of mixed oxides or hydroxides containing iron, cobalt or nickel for inserting or intercalating light metals, e.g. LiNiO2, LiCoO2 or LiCoOxFy
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2002/00—Crystal-structural characteristics
    • C01P2002/20—Two-dimensional structures
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2002/00—Crystal-structural characteristics
    • C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
    • C01P2002/72—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by d-values or two theta-values, e.g. as X-ray diagram
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2002/00—Crystal-structural characteristics
    • C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
    • C01P2002/76—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by a space-group or by other symmetry indications
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2002/00—Crystal-structural characteristics
    • C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
    • C01P2002/77—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by unit-cell parameters, atom positions or structure diagrams
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2006/00—Physical properties of inorganic compounds
    • C01P2006/40—Electric properties
    • 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

Definitions

  • An aspect of the present invention relates to a sodium transition metal compound for use in electrodes, used for example in a sodium ion battery application.
  • sodium-ion batteries are analogous in many ways to the lithium-ion batteries that are in use today; sodium ion batteries are reusable secondary batteries that comprise an anode (negative electrode), a cathode (positive electrode) and an electrolyte material, are capable of storing energy, and they charge and discharge via a similar reaction mechanism to Lithium ion batteries.
  • a metal ion secondary battery lithium or sodium ion battery
  • Na + (or Li + ) ions de-intercalate from the cathode and insert into the anode and charge balancing electrons pass from the cathode through an external circuit and into the anode of the battery. During discharge the same process occurs but in the opposite direction.
  • Lithium-ion battery technology has been the focus of much secondary battery development in recent years and provides the preferred portable battery for most electronic devices.
  • Several limitations have been identified which hinder the uptake of Lithium ion batteries in other applications such as large scale energy storage; these limitations include the cost of Li and the generally high cost of Li cells.
  • sodium-ion battery technology is still in its early stages of development but is seen as advantageous. As sodium is much more abundant than lithium some researchers predict this will provide a cheaper and more sustainable method to store energy into the future, particularly for large scale energy storage applications.
  • further development and optimisation of sodium ion technology is required before commercialisation of the technology is a reality.
  • An aspect of this invention discloses novel material compositions based on a layered oxide framework. Most of the background literature for this class of material is based upon stoichiometric sodium transition metal oxides which adopt either a P2 or O3 layered structure. An aspect of this invention describes novel compositions based on the sodium layered oxide framework which are stable when charged beyond their theoretical reversible capacity. These novel materials are particularly useful for application in a high energy density sodium ion battery.
  • M includes at least two of manganese (Mn), iron (Fe), cobalt (Co), and nickel (Ni) and forms the positive electrode of a battery to be used in conjunction with a negative electrode.
  • US8835041B2 describes an electrode material suitable for use as a cathode in a sodium electrochemical cell or battery, the electrode comprises a layered material of the formula Na c Li d Ni e Mn f M z O b , wherein M comprises one or more metal cations, 0.24 ⁇ c/b ⁇ 0.5, 0 ⁇ d/b ⁇ 0.23, 0 ⁇ e/b ⁇ 0.45, 0 ⁇ f/b ⁇ 0.45, 0 ⁇ z/b ⁇ 0.45, the combined average oxidation state of the metal components (i.e., Na c Li d Ni e Mn f M z ) is in the range of about 3.9 to 5.2, and b is equal to (c+d+Ve+Xf+Yz)/2, wherein V is the average oxidation state of the
  • the combined positive charge of the metallic elements is balanced by the combined negative charge of the oxygen anions, the Na is predominately present in a sodium layer, and the Li, Mn, Ni, and M are predominately present in a transition metal layer.
  • the index “1”, “2”, “i” in M 1 , M 2 and M i is used to denote a particular constituent, and is not related to the oxidation state of the constituent.
  • transition metal as used herein includes the d-block elements, groups 3 to 12 of the periodic table.
  • a transition metal in a +4 oxidation state, a lanthanide in a +4 oxidation state, an actinide in a +4 oxidation state, or a mixture thereof includes for example a mixture of two or more different transition metals each in a +4 oxidation state, a mixture of two or more different lanthanides each in a +4 oxidation state, a mixture of two or more different actinides each in a +4 oxidation state, a mixture of at least one transition metal in a +4 oxidation state and at least one lanthanide in a +4 oxidation state, etc.
  • Z may be sodium or may be a mixture of sodium and lithium.
  • the composition may have the formula: Na 1 Z’ + y-c Na c Ni 2+ 1/4 M 2 7/12 O 2 ⁇ d where Z’ is a group 1 element other than sodium and 0 ⁇ c ⁇ y.
  • M 2 may comprise one or more elements selected from the list consisting of: Mn, Ti, Mo and Zr.
  • the M 2 constituent is not however limited to these elements.
  • the M 2 constituent may additionally or alternatively include Nb 4+ and/or Ce 4+ .
  • a material of the invention may have a layered oxide structure in which the group 1 metal atoms Z are co-ordinated by oxygen in a prismatic environment, or a layered oxide structure in which the group 1 metal atoms Z are co-ordinated by oxygen in an octahedral environment.
  • a second aspect of the invention provides an electrode comprising a composition of the first aspect.
  • a third aspect of the invention provides an electrochemical cell comprising an electrode of the second aspect.
  • the electrochemical cell may exhibit a reversible charge voltage against a sodium metal anode having a plateau at about 4.1 to 4.5 V vs Na/Na+ when charged beyond the theoretical capacity of transition metal redox for the M 1 constituent.
  • the theoretical capacity may be determined according to: where Y is the number of electrons transferred per formula unit based on the content of redox active transition metals; N a is Avogadro’s number; Q e is Faraday’s constant; and M w is the molecular weight of the compound.
  • a fourth aspect of the invention provides a method of preparing a compound as defined in the first aspect, the method comprising the steps of: a) mixing precursor materials together, b) heating the mixed precursor materials in a furnace at a temperature of between 400°C and 1500°C, for between 2 and 20 hours; and c) allowing the reaction product to cool.
  • a fifth aspect of the invention provides a method comprising charging a material having a composition as defined in the first aspect to a capacity greater than a theoretical charging capacity determined from the content of redox active elements in the material.
  • a sixth aspect of the invention provides a use of a material having a composition as defined in as defined in the first aspect, the use comprising charging the material to a capacity greater than a theoretical charging capacity determined from the content of redox active elements in the material.
  • the theoretical capacity may be determined according to equation (1) above.
  • the material may be charged to a specific capacity (expressed as charge stored per unit mass of material) that is at least 10% greater than the theoretical charging capacity, where the percentage increase is defined as 100 x (O - T)/T where O is the observed specific charging capacity and T is the theoretical specific charging capacity. Equivalently, the increase in the charging capacity may be defined as 100 x (A - E)/E where A is the actual number of sodium atoms reversibly intercalated per formula unit and E is the expected number of sodium atoms reversibly intercalated per formula unit determined from the content of redox active elements in the material.
  • the material may be charged to a specific capacity that is at least 15% greater than the theoretical charging capacity, or that is at least 20% greater than the theoretical charging capacity, or that is at least 30% greater than the theoretical charging capacity, or that is at least 40% greater than the theoretical charging capacity, or that is at least 50% greater than the theoretical charging capacity.
  • Figure 1(A) shows the Powder X-ray diffraction pattern of Na Ni 1/4 Na 1/6 Mn 4/12 Ti 3/12 O 2 prepared according to Example 1
  • FIGURE 1(B) shows the cell voltage profile (Voltage [Vs Na/Na + ] versus Cumulative Cathode Specific Capacity [mAh/g]) for the first ten charge/discharge cycles Na Ni 1/4 Na 1/6 Mn 4/12 Ti 3/12 O 2 cycled in a sodium metal cell
  • Figure 2(A) shows Powder X-ray diffraction pattern of Na Ni 1/4 Na 1/6 Mn 2/12 Ti 5/12 O 2 prepared according to Example 2
  • FIGURE 2(B) shows the cell voltage profile (Voltage [Vs Na/Na + ] versus Cumulative Cathode Specific Capacity [mAh/g]) for the first ten charge/discharge cycles of Na Ni 1/4 Na 1/6 Mn 2/12 Ti 5/12 O 2 cycled in a sodium metal cell
  • Figure 3(A) shows Powder X-ray diffraction pattern
  • An aspect of the invention relates to electrodes for sodium and sodium-ion cells and batteries comprising layered transition metal oxide materials of the general formula set out above.
  • the oxidation states present in the material may or may not be integers i.e. they may be whole numbers or fractions or a combination of whole numbers and fractions and may be averaged over different crystallographic sites in the material.
  • transition metal as used herein includes the d-block elements, groups 3 to 12 of the periodic table.
  • the composition may adopt a layered oxide structure in which the alkali metal atoms X are co-ordinated by oxygen in a prismatic environment, or it may adopt a layered oxide structure in which the alkali metal atoms X are co-ordinated by oxygen in an octahedral environment.
  • layered oxides of the form ABO 2 can exist as several structural polymorphs, where layers of edge sharing octahedrally coordinated B cations (BO 6 ) are stacked perpendicular to layers of Prismatic or octahedrally coordinated “A” cations.
  • A is generally an alkali metal atom and B is generally a transition metal atom.
  • the electrode material has a layered oxide structure with the structure notation ABO 2 in which element(s) A occupy one site and have an oxidation state of +1, and in which element(s) B occupy another site and have an average oxidation state of +3.
  • element X of the composition X w M 1 x Z y M 2 z2 M i zi O 2 ⁇ d is predominantly found in site A of the ABO 2 notation, and elements M 1 , Z, M 2 , and any further M i that are present, are predominantly found in site B of the ABO 2 notation.
  • the ratio of elements may deviate from the ideal ABO 2 stoichiometry to give a composition with the non-stoichiometric formula ABO 2 ⁇ , with the average oxidation state of one or more elements contained within site B being less than or greater than +3 to retain charge neutrality.
  • the proportion of elements on the B site does not change, and there is variation in occupancy on the O site only. So the relative proportions of elements within the material can be expressed as 1:1:(2 ⁇ ⁇ ).
  • the complex oxide of an aspect of the invention is of the formula Na 1+c X + 1/6-c Ni 2+ 1/4 M 2 7/12 O 2 ⁇ d where X is a group 1 element.
  • An aspect of the present invention provides electrodes containing novel layered oxide materials which display surprisingly high reversible capacities when the transition metal redox capacity of the material is considered alone.
  • An electrochemical cell of an aspect of the present invention comprises an electrode of an aspect of the invention as a cathode, in combination with an anode, and a sodium-containing electrolyte there between.
  • the electrochemical cell exhibits a reversible charge voltage plateau at about 4.1 to 4.5 V vs Na/Na+ when charged beyond the theoretical capacity of transition metal redox.
  • Preferred compounds of an aspect of the present invention include: Na Ni 1/4 Na 1/6 Mn 7/12 O 2 Na Ni 1/4 Na 1/6 Ti 7/12 O 2 Na Ni 1/4 Na 1/6 Mn 7/12-x Ti x O 2 Na Ni 1/4 Na 1/6 Mn 7/12-x Ti x O 2 Na Ni 1/4 Na 1/6 Mn 7/12-x Zr x O 2 Na Ni 1/4 Na 1/6 Mn 7/12-x Mo x O 2 Na Ni 1/4 Na 1/6 Mn 7/12-x+y Ti x Zr y O 2 Na Ni 1/4 Na 1/6 Mn 7/12-x+y Ti x Mo y O 2 NaNi 1/4 Na 1/6-y Li y Mn 1-x Ti x O 2 NaNi 1/4 Na 1/6-y Li y Mn 7/12-x Zr x O 2 NaNi 1/4 Na 1/6-y Li y Mn 7/12-x Mo x O 2 NaNi 1/4 Na 1/6-y Li y Mn 7/12-x Zr x O 2 NaNi 1/4 Na 1/6-y Li y M
  • Group 1 elements are considered electrochemically inactive, the addition of these elements to the transition metal layer (Site B) has been found by the inventors to have a stabilising effect on the structure of the active materials used in the electrodes of an aspect of the present invention. This yields higher than expected reversible capacities. It is believed that the addition of Group 1 elements to the transition metal layers reduces or eliminates oxygen loss from the materials when they are overcharged or charged beyond their theoretical reversible capacity. Further, the applicant has found electrodes of an aspect of the present invention show excellent electrochemical stability on cycling; resulting in batteries which are capable of being charged and recharged numerous times.
  • Electrodes of an aspect of the present invention are suitable for use in many different applications, for example energy storage devices, rechargeable batteries, electrochemical devices, catalysts and electrochromic devices.
  • electrodes of an aspect of the present invention are used in conjunction with a counter electrode and one or more electrolyte materials.
  • the electrolyte materials may be any conventional or known materials and may comprise either aqueous electrolyte(s) or non-aqueous electrolyte(s) or mixtures thereof.
  • the compounds of an aspect of the present invention may be prepared using any known and/or convenient method.
  • the precursor materials may be heated in a furnace to facilitate a solid state reaction.
  • a second aspect of the invention provides an electrode comprising a composition according to the first aspect.
  • the composition may form an active element of the electrode.
  • An electrode of this aspect may be used in conjunction with a counter electrode and one or more electrolyte materials.
  • the electrolyte material may comprise an aqueous electrolyte material, or it may comprise a non-aqueous electrolyte.
  • a third aspect of the invention provides an energy storage device comprising an electrode of the second aspect.
  • the energy storage device may be suitable for use as one or more of the following: a sodium ion cell; a sodium metal cell; a non-aqueous electrolyte sodium ion cell; and an aqueous electrolyte sodium ion cell.
  • a fourth aspect of the invention provides a rechargeable battery comprising at least one of an electrode of the second aspect and an energy storage device of the third aspect.
  • a fifth aspect of the invention provides an electrochemical device comprising at least one of an electrode of the second aspect and an energy storage device of the third aspect.
  • a sixth aspect of the invention provides an electrochromic device comprising at least one of an electrode of the second aspect and an energy storage device of the third aspect.
  • a seventh aspect of the invention provides an oxide ion conductor comprising a material having a composition according to the first aspect.
  • Another aspect of the invention provides a particularly advantageous method for the preparation of the compounds described above comprising the steps of: a) mixing the starting materials together, preferably intimately mixing the starting materials together and optionally pressing the mixed starting materials into a pellet; b) heating the mixed starting materials in a furnace at a temperature of between 400°C and 1500°C, preferably a temperature of between 500 o C and 1200 o C, for between 2 and 20 hours; and c) allowing the reaction product to cool.
  • reaction is conducted under an atmosphere of ambient air, and alternatively under an inert gas.
  • a suitable method for synthesising a compound according to the present invention required amounts of the precursor materials are intimately mixed together and either pressed into a pellet or retained as a free flowing powder.
  • the resulting mixture is then heated in a tube furnace or a chamber furnace using either an ambient air atmosphere, or a flowing inert atmosphere (e.g. argon or nitrogen), at a furnace temperature of between 400°C and 1500°C until reaction product forms; for some materials a single heating step is used and for others (as indicated below in Table 1) more than one heating step is used.
  • a flowing inert atmosphere e.g. argon or nitrogen
  • Electrochemical cells were prepared using conventional electrochemical testing techniques. Materials were tested as cast electrodes. To prepare an electrode of the test material the sample was cast using a solvent-casting technique, from a slurry containing the active material, conductive carbon, binder and solvent. The conductive carbon used is Super P C65 (Timcal), PVdF is used as the binder, and NMP (N-Methyl-2-pyrrolidone , Anhydrous, Sigma, UK) is used as the solvent. The slurry is then cast onto an aluminium current collector using the Doctor-blade technique. The electrode is then dried under Vacuum at about 80 - 120°C for about 4 hours.
  • the electrode film contains the following components, expressed in percent by weight: 75% active material, 18% Super P carbon, and 7% binder. Optionally, this ratio can be varied to optimise the electrode properties such as, adhesion, resistivity and porosity.
  • the electrolyte comprises a 0.5 or 1.0 M solution of NaClO 4 in propylene carbonate (PC), and can also be of any suitable or known electrolyte or mixture thereof.
  • a glass fibre separator e.g. Whatman, GF/A
  • a porous polypropylene separator e.g. Celgard 2400
  • Electrochemical cells of materials prepared according to the procedures outlined in Table 1 were tested using Constant Current Cycling Techniques.
  • the cells were cycled at a given current density (ca. 5 - 10 mA/g) between pre-set voltage limits as deemed appropriate for the material under test. This was typically a potential greater than that required to obtain the expected capacity based on transition metal redox.
  • a commercial battery cycler from Maccor Inc. (Tulsa, OK, USA) was used to collect data. Cells were charged symmetrically between the upper and lower voltage limits at a constant current density. On charge sodium ions are extracted from the cathode and migrate to the anode. On discharge the reverse process occurs and Sodium ions are re-inserted into the cathode material.
  • ⁇ X-ray photoelectron Spectroscopy ⁇ X-ray photoelectron spectra were collected using a Thermo K alpha XPS instrument using an Al X-ray source. Cells were constructed as described. Charged Cells (To a given potential) were dismantled in an inert atmosphere, washed 3 times with DMC and transferred into the XPS instrument using an airless transfer method.
  • An aspect of the invention relates to novel material compositions which have high reversible capacities and good electrochemical stability through the substitution of redox inactive elements in specific structural sites, when used in an electrode these materials exhibit a reversible charge/discharge voltage plateau at about 4.1 to 4.5 V vs Na/Na+ if charged beyond the capacity expected from transition metal redox. These materials demonstrate higher than expected reversible capacities and are simultaneously tolerant of charge beyond the theoretical capacity of the material without substantial decomposition of material structure. An aspect of the invention will be described with reference to Example 1 to 6.
  • Example 1 With reference to Example 1.
  • the data shown in Figure 1A shows the Powder X-ray diffraction pattern of Na Ni 1/4 Na 1/6 Mn 4/12 Ti 3/12 O 2 showing the formation of an O3 layered oxide phase.
  • the data shown in Figure 1(B) are derived from the constant current cycling data for Na Ni 1/4 Na 1/6 Mn 4/12 Ti 3/12 O 2 cathode active material cast as an electrode in a Na metal half cell.
  • the electrolyte used was a 0.5 M solution of NaClO 4 in propylene carbonate (PC).
  • the constant current data were collected at an approximate current of 10 mA/g between voltage limits of 1.50 and 4.3 V Vs Na/Na + and the testing was undertaken at room temperature (ca. 22 °C).
  • sodium ions are extracted from the cathode active material, and plated/deposited onto the Na metal anode.
  • Figure 1(B) shows the cell voltage profile (Cell Voltage [V] versus Cumulative Cathode Specific Capacity [mAh/g]) for the first ten charge/discharge cycles of Na Ni 1/4 Na 1/6 Mn 4/12 Ti 3/12 O 2 cycled in a sodium metal cell.
  • Cell Voltage [V] Cumulative Cathode Specific Capacity [mAh/g]
  • Example 1 shows a number of key benefits over the current state of the art.
  • the material exceeds the maximum capacity which can be attributed to transition metal redox (i.e.
  • Example 2 With reference to Example 2, The data shown in Figure 2A is the Powder X-ray diffraction pattern of Na Ni 1/4 Na 1/6 Mn 2/12 Ti 5/12 O 2 showing the formation of an O3 layered oxide phase.
  • This material is a compositional variant of Example 1 in which further element substitution in the transition metal site has yielded the same material structure. Further atomic substitution within this material was demonstrated as it can significantly influence commercial factors such as cost.
  • Na Ni 1/4 Na 1/6 Mn 2/12 Ti 5/12 O 2 showed a reversible capability of 185 mAh/g this equates to the reversible intercalation of 0.7 Na atoms per formula unit which is comparable to that observed in Example 1.
  • transition metal redox i.e. the oxidation of Ni from Ni 2+ to Ni 4+
  • a reversible intercalation of 0.7 Na atoms per formula unit, compared to an expected intercalation of 0.5 Na per formula unit corresponds to an increase of 40% - and the increase in specific capacity would be approximately the same as this.
  • Example 1 shows a capacity in excess of that expected by theoretical calculation.
  • Analysis of the voltage profiles shown in Figure 2(B) suggest that the enhancement of capacity is again related to the high voltage redox processes occurring at > 4.0 V Vs Na/Na + . These high voltage redox processes have significant positive effects on the specific energy of the cell by increasing the average intercalation and de-intercalation potentials.
  • Example 3 With reference to Example 3, The data shown in Figure 3A is the Powder X-ray diffraction pattern of Na Ni 1/4 Na 1/6 Mn 5/12 Ti 2/12 O 2 showing the formation of an O3 layered oxide phase.
  • This material is a compositional variant of Example 1 and Example 2 in which further element substitution in the transition metal site has yielded the same material structure.
  • the data shown in Figure 3(B) is taken from the constant current cycling of an electrode containing Na Ni 1/4 Na 1/6 Mn 5/12 Ti 2/12 O 2 as the cathode active material in a Na metal half cell.
  • the constant current data were collected at an approximate current density of 10 mA/g between voltage limits of 1.50 and 4.3 V Vs Na/Na + and the testing was undertaken at room temperature (ca. 22 °C) consistent with the characterisation of Examples 1 and 2. It can be seen in Figure 3(B) that further substitution within the layered oxide frame work was not detrimental to the electrochemical performance of the material when compared with the other Example electrode materials.
  • Na Ni 1/4 Na 1/6 Mn 5/12 Ti 2/12 O 2 showed a reversible capacity of 175 mAh/g this equates to the reversible intercalation of 0.66 Na atoms per formula unit which is comparable to that observed in Examples 1 and 2.
  • transition metal redox i.e. the oxidation of Ni from Ni 2+ to Ni 4+
  • this material shows a capacity in excess of that expected by theoretical calculation.
  • Example 4 With reference to Example 4, The data shown in Figure 4A is the Powder X-ray diffraction pattern of Na Ni 1/4 Na 1/6 Mn 1/12 Ti 6/12 O 2 which also shows that this composition crystalises into an O3 layered oxide phase, consistent with other examples of the present invention.
  • Example 5 With reference to Example 5, which is a further compositional variant of Example 1-4.
  • the data shown in Figure 5 (A) is the Powder X-ray diffraction pattern of Na Ni 1/4 Mn 7/12 Na 1/12 Li 1/12 O 2 which also shows that this composition crystalises into an O3 layered oxide phase.
  • Example 6 is another compositional variant of Examples 1-4.
  • the data shown in Figure 6 (A) is the Powder X-ray diffraction pattern of Na Ni 1/4 Mn 7/12 Na 3/24 Li 1/24 O 2 which also shows that this composition crystalises into an O3 layered oxide phase.
  • Na Ni 1/4 Mn 7/12 Na 3/24 Li 1/24 O 2 shows partial substitution of Na for Li in the structure and demonstrates a reversible capacity of 171 mAh/g, this equates to the reversible intercalation of 0.65 Na atoms per formula unit which is again commensurate with that observed in the other examples of an aspect of the invention. Again, this material demonstrated a reversible capacity far greater than that expected from transition metal redox (i.e. the oxidation of Ni from Ni 2+ to Ni 4+ ) which would be expected to yield reversible intercalation of 0.5 Na per formula unit.
  • transition metal redox i.e. the oxidation of Ni from Ni 2+ to Ni 4+
  • Electrodes of an aspect of the present invention are characterised as containing the disclosed electrochemically active cathode materials, a conductive additive (e.g. Carbon), and a polymer binder; in combination these materials exhibit a reversible charge/discharge voltage plateau at about 4.1 to 4.5 V vs Na/Na+ if charged beyond the capacity expected from transition metal redox.
  • a conductive additive e.g. Carbon
  • Electrochemically active materials of an aspect of the described invention are characterised as having one or more Alkali Metals substituted into the transition metal layer (or B site in the ABO 2 classification of these structures). In this position the alkali metals are considered electrochemically inactive and predominantly remain in the structure during electrochemical reaction.
  • the addition of these elements to the transition metal layer (Site B) has a stabilising effect on the structure of the active materials used in the electrodes of an aspect of the present invention. This yields higher than expected reversible capacities.
  • the structure of the materials disclosed here will now be discussed with reference to the examples.
  • Example 3 has the composition Na Ni 1/4 Na 1/6 Mn 5/12 Ti 2/12 O 2 in which approximately 1 Na atom is located in the A site of the material and in which approximately 0.1667 Na atoms are located in the B site per formula unit. In the material the remainder of the occupancy of the B site is filled by other substituents. In Example 3 approximately 0.8333 transition metal or other atoms occupy the remainder of the B site per formula unit.
  • Table 2 provides a summary of the structural parameters obtained from the material by structure determination using the Rietveld method fitting to the space group R-3m.
  • Table 3 provides a summary of the occupancy of atoms in the different crystallographic sites for Na Ni 1/4 Na 1/6 Mn 5/12 Ti 2/12 O 2 in the space group R-3m. From this data it is possible to conclude that Na resides on two discrete sites in the crystal structure of Na Ni 1/4 Na 1/6 Mn 5/12 Ti 2/12 O 2 (Example 3) confirming the occupancy by Na of both the A site and the B site as described above.
  • Table 2 Summary of the structural parameters obtained for Na Ni 1/4 Na 1/6 Mn 5/12 Ti 2/12 O 2 (Example 3) by structure determination using the Rietveld method
  • Figure 7(A) shows X-ray diffraction measurements showing the effect of charging Na Ni 1/4 Na 1/6 Mn 5/12 Ti 2/12 O 2 (Example 3) to a potential of up to 4.3V Vs Na/Na + on the structure of the material.
  • Table 4 provides a summary of the structural parameters obtained from the material formed after the first electrochemical cycle of Na Ni 1/4 Na 1/6 Mn 5/12 Ti 2/12 O 2 (Example 3) by structure determination using the Rietveld method fitting to the space group R-3m. Further to the data provided in Table 4 it is also possible to determine the position of atoms and their relative abundance in each site of the material.
  • Table 5 provides a summary of the occupancy of atoms in the different crystallographic sites of Example 3 after the first electrochemical cycle determined using the space group R-3m. This data demonstrates that Na maybe retained within the B site after the first electrochemical cycle. It is this feature which we believe is responsible for the materials showing higher reversible capacities as the structure does not appear to decompose when charged beyond the theoretical capacity. This feature is observed in Examples 1-6 and this unique feature appears to persist over many electrochemical cycles as described in the examples.
  • Table 4 Summary of the structural parameters obtained for Na Ni 1/4 Na 1/6 Mn 5/12 Ti 2/12 O 2 (Example 3) by structure determination using the Rietveld method after the first electrochemical cycle.
  • Example 3 it is also possible to further clarify the performance of Example 3. For example it can be resolved that the co-ordination of Oxygen in the materials changes as a function of charge by studying the bonding of oxygen within the material as a state of charge using XPS (X-ray photoelectron spectroscopy).
  • XPS X-ray photoelectron spectroscopy
  • Figures 8A-D the photoelectron spectrum of the O1s orbital is shown for the material Na Ni 1/4 Na 1/6 Mn 5/12 Ti 2/12 O 2 (Example 3) as a function of potential. This data was collected by ex-situ testing of the cells. From this figure it can be seen that the distribution of binding energies of oxygen change within the material as a function of state of charge which is indicative of oxygen rearrangement occurring in the material.
  • Figure 8A shows the O1s photoelectron spectrum of Na Ni 1/4 Na 1/6 Mn 5/12 Ti 2/12 O 2 (Example 3) charged to a potential of 3.8 V vs Na/Na + .
  • Deconvolution of this spectrum shows approximately three binding energies associated with oxygen in the material as demarked on Figure 8A.
  • the three assigned binding energies in this sample are attributed to; Electrolyte oxidation (ca. 533.5 eV), Lattice oxygen species of the type O 2- (ca. 529.5 eV) and surface oxidised species (ca. 531.6 eV).
  • oxygen non-stoichiometry as deviation from the ABO 2 formula of the layered oxide framework to give a compound with the formula ABO 2 ⁇ d , wherein, the average oxidation state of one or more elements contained within the B site reduces or increases to rebalance the structure’s charge and retain charge neutrality whilst the proportion of elements on the B site remains unchanged.
  • mixtures of precursor materials can be heated to a suitable reaction temperature under an atmosphere of nitrogen or other inert non-oxidising gas.
  • oxygen deficient materials of the present invention could be produced by heating mixtures of precursors under an oxidising atmosphere until the reaction product forms and then quenching to room temperature under a non-oxidising atmosphere such as nitrogen or argon.
  • oxygen rich materials of the present invention requires that the oxidation state of one of the transition metals be raised in general or that the valence of oxygen reduces through peroxide or superoxide bond formation.
  • mixtures of precursor materials can for example be heated to a suitable reaction temperature under a saturated oxygen atmosphere and quenched to room temperature.
  • Electrodes according to an aspect of the present invention are suitable for use in many different applications, energy storage devices, rechargeable batteries, electrochemical devices, catalysts and electrochromic devices.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Manufacturing & Machinery (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Environmental & Geological Engineering (AREA)
  • General Life Sciences & Earth Sciences (AREA)
  • Geology (AREA)
  • Battery Electrode And Active Subsutance (AREA)
  • Secondary Cells (AREA)

Abstract

La présente invention concerne une composition comprend la formule générale Xw M1 x Zy M2 z2 Mi zi O2±d : dans laquelle x est du sodium dans un état d'oxydation +1 ou un mélange de métaux du groupe 1 dans un état d'oxydation +1 comprenant du sodium en tant que constituant principal, et 0 < w ; M1 est un métal de transition dans un état d'oxydation +2 et 0,05 ≦ x ≦ 0,5 ; Z est un élément du groupe 1, ou un mélange d'éléments du groupe 1, mais à l'exclusion de Li en tant que constituant unique, et 0,01 ≦ y ≦ 0,5 ; M2 est un métal de transition dans un état d'oxydation +4, un lanthanide dans un état d'oxydation +4, un actinide dans un état d'oxydation +4, ou un mélange correspondant, et z2 > 0 ; Mi pour i = 3, 4... n, est un métal de transition, un lanthanide, un actinide, un métal alcalino-terreux, de l'aluminium, du gallium, de l'indium, du thallium, du germanium, du plomb, de l'antimoine ou du bismuth, ou un mélange correspondant, et zi ≧ 0 pour chaque i = 3, 4... n ; et d ≦ 0,2. Il a été découvert que ces matériaux peuvent être chargés à une capacité qui est supérieure à la capacité de charge théorique du matériau, tel que déterminé à partir de la teneur en éléments à activité redox dans le matériau.
PCT/JP2016/003436 2015-07-24 2016-07-22 Composés d'oxydes de métaux de transition à base de sodium pour batteries na-ion Ceased WO2017017944A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
GB1513118.8 2015-07-24
GB1513118.8A GB2540626A (en) 2015-07-24 2015-07-24 Sodium transition metal oxide compounds for na-ion batteries

Publications (1)

Publication Number Publication Date
WO2017017944A1 true WO2017017944A1 (fr) 2017-02-02

Family

ID=54106600

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/JP2016/003436 Ceased WO2017017944A1 (fr) 2015-07-24 2016-07-22 Composés d'oxydes de métaux de transition à base de sodium pour batteries na-ion

Country Status (2)

Country Link
GB (1) GB2540626A (fr)
WO (1) WO2017017944A1 (fr)

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN112490398A (zh) * 2021-01-22 2021-03-12 江西省钒电新能源有限公司 一种p2型钠离子电池层状正极材料及制备方法和应用
CN113937286A (zh) * 2020-06-29 2022-01-14 溧阳中科海钠科技有限责任公司 一种包覆改性的钠离子电池正极材料及其制备方法和电池
CN115207339A (zh) * 2022-08-25 2022-10-18 江苏正力新能电池技术有限公司 一种正极材料及其制备方法、正极极片和o3型层状钠离子电池

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
RU2761861C1 (ru) * 2021-05-19 2021-12-13 Федеральное государственное бюджетное учреждение науки Институт физической химии и электрохимии им. А.Н. Фрумкина Российской академии наук (ИФХЭ РАН) Анод натрий-ионного аккумулятора и способ его изготовления

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2006024486A (ja) * 2004-07-09 2006-01-26 Nippon Telegr & Teleph Corp <Ntt> Ｌｉ−Ｎｉ−Ｔｉ複合酸化物電極材料の製造方法およびその電極材料を用いた電池
WO2014009710A1 (fr) * 2012-07-10 2014-01-16 Faradion Ltd Composés de nickelate dopés
WO2014077662A1 (fr) * 2012-11-19 2014-05-22 한양대학교 산학협력단 Procédé permettant de produire un précurseur de matière active d'anode pour batterie secondaire au sodium en utilisant une technique de coprécipitation et précurseur de matière active d'anode pour batterie secondaire au sodium produite ainsi
WO2015177568A1 (fr) * 2014-05-22 2015-11-26 Faradion Limited Composés contenant de l'étain
CN105226264A (zh) * 2014-06-16 2016-01-06 北京理工大学 一种钠离子电池富钠正极材料及其制备方法和钠离子电池
WO2016103693A1 (fr) * 2014-12-23 2016-06-30 Sharp Kabushiki Kaisha Compositions d'oxyde stratifiées

Family Cites Families (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP1826845A4 (fr) * 2004-11-26 2010-12-15 Sumitomo Chemical Co Materiau actif d'electrode positive destine a une batterie secondaire d'electrolyte non aqueux
KR20100120138A (ko) * 2008-02-04 2010-11-12 스미또모 가가꾸 가부시키가이샤 복합 금속 산화물 및 나트륨 이차 전지
GB2503896A (en) * 2012-07-10 2014-01-15 Faradion Ltd Nickel doped compound for use as an electrode material in energy storage devices
WO2014115772A1 (fr) * 2013-01-23 2014-07-31 学校法人東京理科大学 Oxyde métallique combiné, substance active pour électrode positive pour batterie rechargeable au sodium, électrode positive pour batterie rechargeable au sodium et batterie rechargeable au sodium
CN103531778A (zh) * 2013-10-28 2014-01-22 北京理工大学 一种固溶体钠离子电池正极材料及其制备方法
GB201400347D0 (en) * 2014-01-09 2014-02-26 Faradion Ltd Doped nickelate compounds

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2006024486A (ja) * 2004-07-09 2006-01-26 Nippon Telegr & Teleph Corp <Ntt> Ｌｉ−Ｎｉ−Ｔｉ複合酸化物電極材料の製造方法およびその電極材料を用いた電池
WO2014009710A1 (fr) * 2012-07-10 2014-01-16 Faradion Ltd Composés de nickelate dopés
WO2014077662A1 (fr) * 2012-11-19 2014-05-22 한양대학교 산학협력단 Procédé permettant de produire un précurseur de matière active d'anode pour batterie secondaire au sodium en utilisant une technique de coprécipitation et précurseur de matière active d'anode pour batterie secondaire au sodium produite ainsi
WO2015177568A1 (fr) * 2014-05-22 2015-11-26 Faradion Limited Composés contenant de l'étain
CN105226264A (zh) * 2014-06-16 2016-01-06 北京理工大学 一种钠离子电池富钠正极材料及其制备方法和钠离子电池
WO2016103693A1 (fr) * 2014-12-23 2016-06-30 Sharp Kabushiki Kaisha Compositions d'oxyde stratifiées

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
TSUDA, M. ET AL.: "Electrode performance of layered LiNi0.5Ti0.5O2 prepared by ion exchange", JOURNAL OF POWER SOURCES, vol. 144, no. 1, 1 June 2005 (2005-06-01), pages 183 - 190, XP025268705, ISSN: 0378-7753 *

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN113937286A (zh) * 2020-06-29 2022-01-14 溧阳中科海钠科技有限责任公司 一种包覆改性的钠离子电池正极材料及其制备方法和电池
CN113937286B (zh) * 2020-06-29 2023-08-29 溧阳中科海钠科技有限责任公司 一种包覆改性的钠离子电池正极材料及其制备方法和电池
CN112490398A (zh) * 2021-01-22 2021-03-12 江西省钒电新能源有限公司 一种p2型钠离子电池层状正极材料及制备方法和应用
CN115207339A (zh) * 2022-08-25 2022-10-18 江苏正力新能电池技术有限公司 一种正极材料及其制备方法、正极极片和o3型层状钠离子电池

Also Published As

Publication number Publication date
GB201513118D0 (en) 2015-09-09
GB2540626A (en) 2017-01-25

Similar Documents

Publication Publication Date Title
EP2872450B1 (fr) Composés nickelate dopés
JP6564397B2 (ja) ドープドニッケル酸塩材料
US9070489B2 (en) Mixed phase lithium metal oxide compositions with desirable battery performance
US20170025678A1 (en) Layered oxide materials for batteries
US9660263B2 (en) Layered oxide materials for batteries
US10263254B2 (en) Tin-containing compounds
US9653731B2 (en) Layered oxide materials for batteries
KR20150030760A (ko) 도핑된 니켈레이트 화합물
KR101352793B1 (ko) 이차전지용 양극재료 및 이의 제조방법
WO2017017944A1 (fr) Composés d&#39;oxydes de métaux de transition à base de sodium pour batteries na-ion
WO2017017943A1 (fr) Composés contenant de l&#39;étain
JP2022554128A (ja) Ｌｍｏカソード組成物
JP2022553967A (ja) Ｌｍｏカソード組成物
HK1206706B (en) Doped nickelate compounds

Legal Events

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

Ref document number: 16830049

Country of ref document: EP

Kind code of ref document: A1

DPE1 Request for preliminary examination filed after expiration of 19th month from priority date (pct application filed from 20040101)
NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 16830049

Country of ref document: EP

Kind code of ref document: A1