(19)
(11)EP 2 828 912 B1

(12)EUROPEAN PATENT SPECIFICATION

(45)Mention of the grant of the patent:
01.07.2020 Bulletin 2020/27

(21)Application number: 13721013.4

(22)Date of filing:  21.03.2013
(51)International Patent Classification (IPC): 
H01M 4/58(2010.01)
C01G 49/00(2006.01)
G02F 1/155(2006.01)
H01M 10/054(2010.01)
C01G 45/00(2006.01)
C01G 53/00(2006.01)
H01M 10/052(2010.01)
C01G 51/00(2006.01)
(86)International application number:
PCT/GB2013/050736
(87)International publication number:
WO 2013/140174 (26.09.2013 Gazette  2013/39)

(54)

METALLATE ELECTRODES

METALLATELEKTRODEN

ÉLECTRODES DE MÉTALLATE


(84)Designated Contracting States:
AL AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HR HU IE IS IT LI LT LU LV MC MK MT NL NO PL PT RO RS SE SI SK SM TR

(30)Priority: 23.03.2012 GB 201205170

(43)Date of publication of application:
28.01.2015 Bulletin 2015/05

(73)Proprietor: Faradion Ltd.
Sheffield S1 4DP (GB)

(72)Inventors:
  • BARKER, Jeremy
    Oxford Oxfordshire OX7 6EH (GB)
  • HEAP, Richard
    Oxford Oxfordshire OX2 9PT (GB)

(74)Representative: Bingham, Ian Mark 
The IP Asset Partnership Limited Prama House 267 Banbury Road
Oxford OX2 7HT
Oxford OX2 7HT (GB)


(56)References cited: : 
EP-A1- 0 583 772
EP-A1- 1 708 296
CN-B- 101 219 811
JP-A- 2007 258 094
US-A1- 2007 218 370
EP-A1- 0 630 064
EP-A2- 2 328 215
JP-A- 2002 050 401
JP-A- 2009 295 290
US-A1- 2011 086 273
  
  • Fernanda M. Costa ET AL: "Preparation and characterization of KTa0.9Fe0.1O3? ? perovskite electrodes", Journal of solid state electrochemistry, vol. 5, no. 7-8, 1 October 2001 (2001-10-01), pages 495-501, XP055109390, ISSN: 1432-8488, DOI: 10.1007/s100080100227
  
Note: Within nine months from the publication of the mention of the grant of the European patent, any person may give notice to the European Patent Office of opposition to the European patent granted. Notice of opposition shall be filed in a written reasoned statement. It shall not be deemed to have been filed until the opposition fee has been paid. (Art. 99(1) European Patent Convention).


Description

FIELD OF THE INVENTION



[0001] The present invention relates to sodium-ion cells.

BACKGROUND OF THE INVENTION



[0002] Sodium-ion batteries are analogous in many ways to the lithium-ion batteries that are in common use today; they are both reusable secondary batteries that comprise an anode (negative electrode), a cathode (positive electrode) and an electrolyte material, both are capable of storing power in a compact system by accumulating energy in the chemical bonds of the cathode, and they both charge and discharge via a similar reaction mechanism. When a sodium-ion (or lithium-ion battery) is charging, Na+ (or Li+) ions de-intercalate and migrate towards the anode. Meanwhile charge balancing electrons pass from the cathode through the external circuit containing the charger and into the anode of the battery. During discharge the same process occurs but in the opposite direction. Once a circuit is completed electrons pass back from the anode to the cathode and the Na+ (or Li+) ions travel back to the anode. Lithium-ion battery technology has enjoyed a lot of attention in recent years and provides the preferred portable battery for most electronic devices in use today; however lithium is not a cheap metal to source and is too expensive for use in large scale applications. By contrast sodium-ion battery technology is still in its relative infancy but is seen as advantageous; sodium is much more abundant than lithium and researchers predict this will provide a cheaper and more durable way to store energy into the future, particularly for large scale applications such as storing energy on the electrical grid. Nevertheless a lot of work has yet to be done before sodium-ion batteries are a commercial reality.

[0003] From the prior art, for example in the Journal of Solid State Chemistry 180 (2007) 1060-1067, L. Viciu et al disclosed the synthesis, structure and basic magnetic properties of Na2Co2TeO6 and Na3Co2SbO6. Also in Dalton Trans 2012, 41, 572, Elena A. Zvereva et al disclosed the preparation, crystal structure and magnetic properties of Li3Ni2SbO6. Neither of these documents discusses the use of such compounds as electrode materials in sodium- or lithium-ion batteries.

[0004] Fernanda M. Costa et al have also reported the "Preparation and Characterisation of KTa0.9Fe0.1O3-δ perovskite electrodes" in the Journal of Solid State Electrochemistry, vol. 5, no. 7-8, 21 July 2001 (2001-07-21), pages 495-501. However, this document is concerned with the use of these materials in photoelectric cells which are energy conservation devices. In particular, photoelectric cells produce an electrical output that varies in response to incident radiation, for example visible light.

[0005] Further, EP0630 064 A1 discloses a lithium ion non-aqueous electrolyte secondary battery which comprises a cathode active material of the formula: LixAyMzJmOp, in which A is one or more from Na and K, M is one or more from Co, Mn and Ni, J is one or more from B, Si, Ge, P, V, Zr, Sb, and Ti, and 0.8 ≤ z ≤ 2.0, 0.01 ≤ m ≤ 0.2, and 2.0 ≤ p ≤ 4.7.

[0006] In a first aspect, the present invention aims to provide a sodium ion cell which comprises a cost effective electrode that contains an active material that is straightforward to manufacture and easy to handle and store. A further object of the present invention is to provide a sodium ion cell which comprises an electrode that has a high initial charge capacity and which is capable of being recharged multiple times without significant loss in charge capacity.

[0007] Therefore, the present invention provides a sodium ion cell comprising a cathode electrode that contains an active material of the formula:

        AaMbXxOy

wherein

A is selected from sodium, or a mixture of sodium and potassium, or a mixture of sodium and lithium;

M is selected from one or more transition metals and/or one or more non-transition metals and/or one or more metalloids;

X comprises one or more atoms selected from niobium, antimony, tellurium, tantalum, bismuth and selenium;

wherein
0<a ≤ 6; b is in the range: 0 < b ≤ 4; x is in the range 0 < x ≤ 1 and y is in the range 2 ≤ y ≤ 10;
and further wherein M comprises one or more transition metals and/or one or more non-transition metals and/or one or more metalloids selected from titanium, vanadium, chromium, molybdenum, tungsten, manganese, iron, osmium, cobalt, nickel, palladium, platinum, copper, silver, gold, zinc, cadmium, magnesium, calcium, beryllium, strontium, barium, aluminium and boron. A particularly preferred cathode electrode contains an active material wherein M is selected from one or more of copper, nickel, cobalt, manganese, titanium, aluminium, vanadium, magnesium and iron.

[0008] The term "metalloids" as used herein is intended to refer to elements which have both metal and non-metal characteristics, for example boron.

[0009] In a preferred embodiment, the electrode of the above formula has one or more of a, b, x and y which are integers, i.e. whole numbers. In an alternative embodiment, one or more of a, b, x and y are non-integers, i.e. fractions.

[0010] We have found it advantageous that the electrode contains an active material wherein at least one of the one or more transition metals has an oxidation state of +2 and at least one of the one or more non-transition metals has an oxidation state of + 2.

[0011] Other suitable electrodes contain an active material wherein at least one of the one or more transition metals has an oxidation state of either +2 or +3 and at least one of the one or more non-transition metals has an oxidation state of +3.

[0012] Preferred electrodes contain an active material of the formula: AaMbSbxOy, wherein A is selected from sodium, or a mixture of sodium and potassium, or a mixture of sodium and lithium, and M is one or more metals selected from cobalt, nickel, manganese, titanium, iron, copper, aluminium, vanadium and magnesium.

[0013] Alternative preferred electrodes contain an active material of the formula: AaMbTexOy, wherein A is selected from sodium, or a mixture of sodium and potassium, or a mixture of sodium and lithium, and M is one or more metals selected from cobalt, nickel, manganese, titanium, iron, copper, aluminium, vanadium and magnesium.

[0014] As described above it is typical that a may be in the range 0<a ≤ 6; b may be in the range: 0 < b ≤ 4; x may be in the range 0 < x ≤ 1 and y may be in the range 2 ≤ y ≤ 10. Preferably, however, a may be in the range 0< a ≤ 5; b may be in the range 0 ≤ b ≤ 3; 0.5 ≤ x ≤ 1; and y may be in the range 2 ≤ y ≤ 9. Alternatively, a may be in the range 0 < a ≤ 5; b may be in the range 0 < b ≤ 2; x may be in the range 0 < x ≤ 1; and 2 ≤ y ≤ 8. As mentioned above, one or more of a, b, x and y may be integers or non-integers.

[0015] Extremely beneficial electrochemical results are expected for electrodes that contain one or more active materials: Na3Ni2SbO6, Na3Ni1.5Mg0.5SbO6, Na3Co2SbO6, Na3Co1.5Mg0.5SbO6, Na3Mn2SbO6, Na3Fe2SbO6, Na3Cu2SbO6, Na2AlMnSbO6, Na2AlNiSbO6, Na2VMgSbO6, NaCoSbO4, NaNiSbO4, NaMnSbO4, Na4FeSbO6, Na0.8Co0.6Sb0.4O2, Na0.8Ni0.6Sb0.4O4, Na2Ni2TeO6, Na2Co2TeO6, Na2Mn2TeO6, Na2Fe2TeO6, Na3Ni2-zMgzSbO6 (0 ≤ z ≤ 0.75), Na4NiTeO6, Na2NiSbO5, Na4Fe3SbO9, Na2Fe3SbO8, Na5NiSbO6, Na4MnSbO6, Na3MnTeO6, Na3FeTeO6, Na4Fe1-z(Ni0.5Ti0.5)zSbO6 (0 ≤ z ≤ 1), Na4Fe0.5Ni0.25Ti0.25SbO6, Na4Fe1-z(Ni0.5Mn0.5)zSbO6 (0 ≤ z ≤ 1), Na4Fe0.5Ni0.25Mn0.25SbO6, Na5-zNi1-zFezSbO6 (0 ≤ z ≤ 1), Na4.5Ni0.5Fe0.5SbO6, Na3Ni1.75Zn0.25SbO6, Na3Ni1.75Cu0.25SbO6 and Na3Ni1.50Mn0.50SbO6.

[0016] Sodium ion cells according to the present invention are suitable for use in many different applications, for example energy storage devices, rechargeable batteries, electrochemical devices and electrochromic devices.

[0017] Advantageously, the electrodes used in the sodium cells according to the 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.

[0018] In a second aspect, the present invention provides a novel material of the formula: A3Ni2-zMgzSbO6, wherein A is selected from sodium or a mixture of sodium and potassium, or a mixture of sodium and lithium, and z is in the range 0 < z < 2.

[0019] In a third aspect, the present invention provides a novel material of the formula: Na3Mn2SbO6.

[0020] In a third aspect, the present invention provides a novel material of the formula: Na3Fe2SbO6.

[0021] The active materials used in the present invention may be prepared using any known and/or convenient method. For example, the precursor materials may be heated in a furnace so as to facilitate a solid state reaction process. Further, the conversion of a sodium-ion rich material to a lithium-ion rich material may be effected using an ion exchange process.

[0022] Typical ways to achieve Na to Li ion exchange include:
  1. 1. Mixing the sodium-ion rich material with an excess of a lithium-ion material e.g. LiNO3, heating to above the melting point of LiNO3 (264°C), cooling and then washing to remove the excess LiNO3;
  2. 2. Treating the Na-ion rich material with an aqueous solution of lithium salts, for example 1M LiCI in water; and
  3. 3. Treating the Na-ion rich material with a non-aqueous solution of lithium salts, for example LiBr in one or more aliphatic alcohols such as hexanol, propanol etc.

BRIEF DESCRIPTION OF THE DRAWINGS



[0023] The present invention will now be described with reference to the following drawings in which:

Figure 1A is the XRD of Na3Ni2SbO6 prepared according to Example 1;

Figure 1B shows the Constant current cycling (Cell Voltage versus Cumulative Cathode Specific Capacity) of a Na-ion cell: Hard Carbon // Na3Ni2SbO6 prepared according to Example 1;

Figure 2 is the XRD for Na3Co2SbO6 prepared according to Example 2;

Figure 3 is the XRD for Na3Mn2SbO6 prepared according to Example 3;

Figure 4A is the XRD for Li3Cu2SbO6 prepared according to Example 22 (outside the scope of the present invention);

Figure 4B shows Constant current cycling (Electrode Potential versus Cumulative Specific Capacity) of Li3Cu2SbO6 prepared according to Example 22 (outside the scope of the present invention);

Figure 5A is the XRD of Na2Ni2TeO6 prepared according to Example 28;

Figure 5B shows the Constant current cycling (Electrode Potential versus Cumulative Specific Capacity) of Na2Ni2TeO6 prepared according to Example 28;

Figure 6A is the XRD of Li3Ni2SbO6 prepared according to Example19 (outside the scope of the present invention);

Figure 6B shows the Constant current cycling (Electrode Potential versus Cumulative Specific Capacity) of Li3Ni2SbO6 prepared according to Example 19 (outside the scope of the present invention);

Figure 7A is the XRD of Na3Ni2-zMgzSbO6, where z = 0.00, 0.25, 0.5, and 0.75, prepared according to method of Examples 34a, 34b, 34c, 34d respectively;

Figure 7B shows the Constant current cycling (Cell Voltage versus Cumulative Cathode Specific Capacity) of a Na-ion cell: Hard Carbon // Na3Ni1.5Mg0.5SbO6 prepared according to Example 34c;

Figure 8A is the XRD of Li3Ni1.5Mg0.5SbO6 prepared according to Example 17 (outside the scope of the present invention);

Figure 8B shows the Constant current cycling (Cell Voltage versus Cumulative Cathode Specific Capacity) of a Li-ion cell: Graphite // Li3Ni1.5Mg0.5SbO6 prepared according to Example 17;

Figure 9A is the XRD of Na3Ni1.75Zn0.25SbO6 prepared according to Example 35;

Figure 9B shows the long term Constant current cycling performance (cathode specific capacity versus cycle number) of a Na-ion Cell comprising Carbotron® (Kureha Inc.) Hard Carbon // Na3Ni1.75Zn0.25SbO6 prepared according to Example 35;

Figure 10A is the XRD of Na3Ni1.75Cu0.25SbO6 prepared according to Example 36;

Figure 10B shows the long term constant current cycling performance (cathode specific capacity versus cycle number) of a Na-ion Cell comprising: Hard Carbon // Na3Ni1.75Cu0.25SbO6 prepared according to Example 36;

Figure 11A is the XRD of Na3Ni1.25Mg0.75SbO6 prepared according to Example 34d;

Figure 11B shows the long term constant current cycling performance (cathode specific capacity versus cycle number) of a Na-ion Cell comprising: Hard Carbon // Na3Ni1.25Mg0.75SbO6 prepared according to Example 34d;

Figure 12A is the XRD of Na3Ni1.50Mn0.50SbO6 prepared according to Example 37;

Figure 12B shows the long term constant current cycling performance (cathode specific capacity versus cycle number) of a Na-ion Cell comprising: Hard Carbon // Na3Ni1.50Mn0.50SbO6 prepared according to Example 37;

Figure 13A is the XRD of Li4FeSbO6 prepared according to Example 38 (outside the scope of the present invention);

Figure 13B shows the constant current cycling data for the Li4FeSbO6 active material prepared according to Example 38;

Figure 14A is the XRD of Li4NiTeO6 prepared according to Example 39 (outside the scope of the present invention);

Figure 14B shows the constant current cycling data for the Li4NiTeO6 active material prepared according to Example 39; and

Figure 15A is the XRD of Na4NiTeO6 prepared according to Example 40; and

Figure 15B shows the constant current cycling data for the Na4NiTeO6 prepared according to Example 40.


DETAILED DESCRIPTION



[0024] Active materials used in the present invention are prepared on a laboratory scale using the following generic method:

Generic Synthesis Method:



[0025] The required amounts of the precursor materials are intimately mixed together. The resulting mixture is then heated in a tube furnace or a chamber furnace using either a flowing inert atmosphere (e.g. argon or nitrogen) or an ambient air atmosphere, at a furnace temperature of between 400°C and 1200°C until reaction product forms. When cool, the reaction product is removed from the furnace and ground into a powder.

[0026] Using the above method, active materials used in the present invention were prepared as summarised below in Examples 1-16, 27-30, 34-37, and 40.
EXAMPLETARGET COMPOUND (ID code)STARTING MATERIALSFURNACE CONDITIONS
1 Na3Ni2SbO6 (X0328) Na2CO3 NiCO3 Sb2O3 Air /800°C, dwell time of 8 hours.
2 Na3Co2SbO6 (X0325) Na2CO3 CoCO3 Sb2O3 Air/ 800°C, dwell time of 8 hours.
3 Na3Mn2SbO6 (X0276) Na2CO3 MnCO3 Sb2O3 N2/ 800°C, dwell time of 8 hours.
4 Na3Fe2SbO6 (X0240) Na2CO3 Fe2O3 Sb2O3 N2 /800°C, dwell time of 8 hours.
5 Na3Cu2SbO6 (X0247) Na2CO3 CuO Sb2O3 Air /800°C, dwell time of 8 hours
6 Na2AlMnSbO6 (X0232) Na2CO3 Al(OH)3 MnCO3 Sb2O3 Air / 800°C, dwell time of 8 hours
7 Na2AlNiSbO6 (X0233) Na2CO3 Al(OH)3 NiCO3 Sb2O3 Air / 800°C, dwell time of 8 hours
8 Na2VMgSbO6 (X0245) Na2CO3 V2O3 Mg(OH)2 NaSbO3.3H2O N2 / 800°C, dwell time of 8 hours
9 NaCoSbO4 (X0253) Na2CO3 CoCO3 Sb2O3.3H2O Air / 800°C, dwell time of 8 hours
10 NaNiSbO4 (X0254) Na2CO3, NiCO3, Sb2O3 Air / 800°C, dwell time of 8 hours
11 NaMnSbO4 (X0257) Na2CO3, MnCO3, Sb2O3 Air / 800°C, dwell time of 8 hours
12 Na4FeSbO6 (X0260) Na2CO3 Fe2O3 Sb2O3 Air / 800°C, dwell time of 8 hours
13 Na0.8Co0.6Sb0.4O2 (X0263) Na2CO3 CoCO3 Sb2O3 Air / 800°C, dwell time of 8 hours
14 Na0.8Ni0.6Sb0.4O4 (X0264) Na2CO3 NiCO3 Sb2O3 Air / 800°C, dwell time of 8 hours
15 Na3Ni1.5Mg0.5SbO6 (X0336) Na2CO3 NiCO3 Sb2O3 Mg(OH)2 Air / 800°C, dwell time of 14 hours
16 Na3Co1.5Mg0.5SbO6 (X0331) Na2CO3 CoCO3 Sb2O3 Mg(OH)2 Air / 800°C, dwell time of 14 hours
17 Li3Ni1.5Mg0.5SbO6 (X0368) comparative Li2CO3 NiCO3 Sb2O3 Mg(OH)2 Air / 800°C, dwell time of 8 hours
18 Li3Co2SbO6 (X0222) comparative Na2CO3 CoCO3 Sb2O3 Air / 800°C, dwell time of 8 hours
19 Li3Ni2SbO6 (X0223) comparative Na2CO3 NiCO3 Sb2O3 Air / 800°C, dwell time of 8 hours
20 Li3Mn2SbO6 (X0239) comparative Na2CO3 MnCO3 Sb2O3 Air / 800°C, dwell time of 8 hours
21 Li3Fe2SbO6 (X0241) comparative Li2CO3 Fe2O3 Sb2O3 N2 / 800°C, dwell time of 8 hours
22 Li3Cu2SbO6 (X0303) comparative Li2CO3 CuO Sb2O3 Air / 800°C,dwell time of 8 hours
23 LiCoSbO4 (X0251) comparative Li2CO3 CoO3 Sb2O3 Air / 800°C, dwell time of 8 hours
24 LiNiSbO4 (X0252) comparative Li2CO3 NiCO3 Sb2O3 Air / 800°C, dwell time of 8 hours
25 LiMnSbO4 (X0256) comparative Li2CO3 MnCO3 Sb2O3 Air / 800°C, dwell time of 8 hours
26 Li3CuSbO5 (X0255) comparative Li2CO3 CuO Sb2O3 Air / 800°C, dwell time of 8 hours
27 Na2Co2TeO6 (X0216) Na2CO3 CoCO3 TeO2 Air / 800°C, dwell time of 8 hours
28 Na2Ni2TeO6 (X0217) Na2CO3 NiCO3 TeO2 Air / 800°C, dwell time of 8 hours
29 Na2Mn2TeO6 (X0234) Na2CO3 MnCO3 TeO2 Air / 800°C
30 Na2Fe2TeO6 (X0236) Na2CO3 Fe2O3 TeO2 N2 / 800°C, dwell time of 8 hours
31 Li2Co2TeO6 (X0218) comparative Li2CO3 CoCO3 TeO2 Air / 800°C, dwell time of 8 hours
32 Li2Ni2TeO6 (X0219) comparative Li2CO3 NiCO3 TeO2 Air / 800°C, dwell time of 8 hours
33 Li2Mn2TeO6 (X0235) comparative Li2CO3 MnCO3 TeO2 Air / 800°C, dwell time of 8 hours
34 Na3Ni2-zMgzSbO6 Na2CO3 NiCO3 Mg(OH)2 Sb2O3 Air / 800°C, dwell time of 8 -14 hours
34a Z=0.00 (X0221) =E.g. 1  
34b Z=0.25 (X0372)  
34c Z=0.5 (X0336) =E.g. 15  
34d Z=0.75 (X0373)  
35 Na3Ni1.75Zn0.25SbO6 (X0392) Na2CO3, NiCO3, Sb2O3, ZnO Air / 800°C, dwell time of 8 hours
36 Na3Ni1.75Cu0.25SbO6 (X0393) Na2CO3, NiCO3, Sb2O3, CuO Air / 800°C, dwell time of 8 hours
37 Na3Ni1.50Mn0.50SbO6 (X0380) Na2CO3, NiCO3, Sb2O3, MnO2 Air / 800°C, dwell time of 8 hours
38 Li4FeSbO6 (X1120A) comparative Li2CO3, Fe2O3, Sb2O3 Air / 800°C, dwell time of 8 hours followed by 800°C, for a further 8 hours
39 Li4NiTeO6 (X 1121) comparative Li2CO3, NiCO3, TeO2 Air / 800°C, dwell time of 8 hours
40 Na4NiTeO6 (X1122) Na2CO3, NiCO3, TeO2 Air / 800°C, dwell time of 8 hours

Product Analysis using XRD



[0027] All of the product materials were analysed by X-ray diffraction techniques using a Siemens D5000 powder diffractometer to confirm that the desired target materials had been prepared and to establish the phase purity of the product material and to determine the types of impurities present. From this information it is possible to determine the unit cell lattice parameters.

[0028] The general operating conditions used to obtain the XRD spectra are as follows:

Slits sizes: 1 mm, 1 mm, 0.1 mm

Range: 2θ = 5 ° - 60 °

X-ray Wavelength = 1.5418 Å) (Cu Kα)

Speed: 0.5 or 1.0 second/step

Increment: 0.015 ° or 0.025°


Electrochemical Results



[0029] The target materials were tested in a lithium metal anode test electrochemical cell to determine their specific capacity and also to establish whether they have the potential to undergo charge and discharge cycles. A lithium metal anode test electrochemical cell containing the active material is constructed as follows:

Generic Procedure to Make A Lithium Metal Test Electrochemical Cell



[0030] The positive electrode is prepared by solvent-casting a slurry of the active material, conductive carbon, binder and solvent. The conductive carbon used is Super P™ (Timcal). PVdF co-polymer (e.g. Kynar Flex™ 2801, Elf Atochem Inc.) is used as the binder, and acetone is employed as the solvent. The slurry is then cast onto glass and a free-standing electrode film is formed as the solvent evaporates. The electrode is then dried further at about 80°C. The electrode film contains the following components, expressed in percent by weight: 80% active material, 8% Super P™ carbon, and 12% Kynar flex™ 2801 binder. Optionally, an aluminium current collector may be used to contact the positive electrode. Metallic lithium on a copper current collector may be employed as the negative electrode. The electrolyte comprises one of the following: (i) a 1 M solution of LiPF6 in ethylene carbonate (EC) and dimethyl carbonate (DMC) in a weight ratio of 1:1; (ii) a 1 M solution of LiPF6 in ethylene carbonate (EC) and diethyl carbonate (DEC) in a weight ratio of 1:1; or (iii) a 1 M solution of LiPF6 in propylene carbonate (PC) A glass fibre separator (Whatman™, GF/A) or a porous polypropylene separator (e.g. Celgard™ 2400) wetted by the electrolyte is interposed between the positive and negative electrodes.

Generic Procedure to Make a Hard Carbon Na-ion Cell



[0031] The positive electrode is prepared by solvent-casting a slurry of the active material, conductive carbon, binder and solvent. The conductive carbon used is Super P™ (Timcal). PVdF co-polymer (e.g. Kynar Flex™ 2801, Elf Atochem Inc.) is used as the binder, and acetone is employed as the solvent. The slurry is then cast onto glass and a free-standing electrode film is formed as the solvent evaporates. The electrode is then dried further at about 80°C. The electrode film contains the following components, expressed in percent by weight: 80% active material, 8% Super P™ carbon, and 12% Kynar Flex™ 2801 binder. Optionally, an aluminium current collector may be used to contact the positive electrode.

[0032] The negative electrode is prepared by solvent-casting a slurry of the hard carbon active material (Carbotron™ P/J, supplied by Kureha), conductive carbon, binder and solvent. The conductive carbon used is Super P™ (Timcal). PVdF co-polymer (e.g. Kynar Flex™ 2801, Elf Atochem Inc.) is used as the binder, and acetone is employed as the solvent. The slurry is then cast onto glass and a free-standing electrode film is formed as the solvent evaporates. The electrode is then dried further at about 80°C. The electrode film contains the following components, expressed in percent by weight: 84% active material, 4% Super P™ carbon, and 12% Kynar Flex™ 2801 binder. Optionally, a copper current collector may be used to contact the negative electrode.

Generic Procedure to Make a Graphite Li-ion Cell



[0033] The positive electrode is prepared by solvent-casting a slurry of the active material, conductive carbon, binder and solvent. The conductive carbon used is Super P™ (Timcal). PVdF co-polymer (e.g. Kynar Flex™ 2801, Elf Atochem Inc.) is used as the binder, and acetone is employed as the solvent. The slurry is then cast onto glass and a free-standing electrode film is formed as the solvent evaporates. The electrode is then dried further at about 80°C. The electrode film contains the following components, expressed in percent by weight: 80% active material, 8% Super P™ carbon, and 12% Kynar Flex™ 2801 binder. Optionally, an aluminium current collector may be used to contact the positive electrode.

[0034] The negative electrode is prepared by solvent-casting a slurry of the graphite active material (a crystalline graphite, supplied by Conoco Inc.), conductive carbon, binder and solvent. The conductive carbon used is Super P™ (Timcal). PVdF co-polymer (e.g. Kynar Flex™ 2801, Elf Atochem Inc.) is used as the binder, and acetone is employed as the solvent. The slurry is then cast onto glass and a free-standing electrode film is formed as the solvent evaporates. The electrode is then dried further at about 80°C. The electrode film contains the following components, expressed in percent by weight: 92% active material, 2% Super P™ carbon, and 6% Kynar Flex™ 2801 binder. Optionally, a copper current collector may be used to contact the negative electrode.

Cell Testing



[0035] The cells are tested as follows using Constant Current Cycling techniques.

[0036] The cell is cycled at a given current density between pre-set voltage limits. A commercial battery cycler from Maccor Inc. (Tulsa, OK, USA) is used. On charge, sodium (lithium) ions are extracted from the active material. During discharge, sodium (lithium) ions are re-inserted into the active material.

Results:


Na3Ni2SbO6 Prepared according to Example 1.



[0037] Referring to Figure 1B. The Cell #202071 shows the constant current cycling data for the Na3Ni2SbO6 active material (X0328) made according to Example 1 in a Na-ion cell where it is coupled with a Hard Carbon (Carbotron™ P/J) anode material. The electrolyte used a 0.5 M solution of NaClO4 in propylene carbonate. The constant current data were collected at an approximate current density of 0.05 mA/cm2 between voltage limits of 1.80 and 4.00 V. To fully charge the cell the Na-ion cell was potentiostatically held at 4.0 V at the end of the constant current charging process. The testing was carried out at room temperature. It is shown that sodium ions are extracted from the cathode active material, Na3Ni2SbO6, and inserted into the Hard Carbon anode during the initial charging of the cell. During the subsequent discharge process, sodium ions are extracted from the Hard Carbon and re-inserted into the Na3Ni2SbO6 cathode active material. The first discharge process corresponds to a specific capacity for the cathode of 86 mAh/g, indicating the reversibility of the sodium ion extraction-insertion processes. The generally symmetrical nature of the charge-discharge curves further indicates the excellent reversibility of the system, and the low level of voltage hysteresis (i.e. the voltage difference between the charge and discharge processes) is extremely small, and this also indicates the excellent kinetics of the extraction-insertion reactions. This is an important property that is useful for producing a high rate active material.

Li3Cu2SbO6 Prepared according to Example 22 (comparative).



[0038] Referring to Figure 4B. The Cell #202014 shows the constant current cycling data for the Li3Cu2SbO6 active material (X0303) made according to Example 22. The electrolyte used a 1.0 M solution of LiPF6 in ethylene carbonate (EC) and diethyl carbonate (DEC). The constant current data were collected using a lithium metal counter electrode at an approximate current density of 0.02 mA/cm2 between voltage limits of 3.00 and 4.20 V. The upper voltage limit was increased by 0.1 V on subsequent cycles. The testing was carried out at room temperature. It is shown that lithium ions are extracted from the active material during the initial charging of the cell. A charge equivalent to a material specific capacity of 33 mAh/g is extracted from the active material. The re-insertion process corresponds to 14 mAh/g, indicating the reversibility of the ion extraction-insertion processes. The generally symmetrical nature of the charge-discharge curves further indicates the excellent reversibility of the system. In addition, the level of voltage hysteresis (i.e. the voltage difference between the charge and discharge processes) is extremely small, indicating the excellent kinetics of the extraction-insertion reactions. This is an important property that is useful for producing a high rate active material.

Na2Ni2TeO6 Prepared according to Example 28.



[0039] Referring to Figure 5B. The Cell #201017 shows the constant current cycling data for the Na2Ni2TeO6 active material (X0217) made according to Example 28. The electrolyte used a 0.5 M solution of NaClO4 in propylene carbonate. The constant current data were collected using a lithium metal counter electrode at an approximate current density of 0.02 mA/cm2 between voltage limits of 3.00 and 4.20 V. The upper voltage limit was increased by 0.1 V on subsequent cycles. The testing was carried out at room temperature. It is shown that sodium ions are extracted from the active material during the initial charging of the cell. A charge equivalent to a material specific capacity of 51mAh/g is extracted from the active material.

[0040] It is expected from thermodynamic considerations that the sodium extracted from the Na2Ni2TeO6 active material during the initial charging process, enters the electrolyte, and would then be displacement 'plated' onto the lithium metal anode (i.e. releasing more lithium into the electrolyte). Therefore, during the subsequent discharging of the cell, it is assumed that a mix of lithium and sodium ions is re-inserted into the active material. The re-insertion process corresponds to 43 mAh/g; indicating the reversibility of the ion extraction-insertion processes. The generally symmetrical nature of the charge-discharge curves further indicates the excellent reversibility of the system. In addition, the level of voltage hysteresis (i.e. the voltage difference between the charge and discharge processes) is extremely small, indicating the excellent kinetics of the extraction-insertion reactions. This is an important property that is useful for producing a high rate active material.

Li3Ni2SbO6 Prepared according to Example 19. (comparative)



[0041] Referring to Figure 6B. The Cell #201020 shows the constant current cycling data for the Li3Ni2SbO6 active material (X0223) made following Example 19. The electrolyte used a 1.0 M solution of LiPF6 in ethylene carbonate (EC) and diethyl carbonate (DEC). The constant current data were collected using a lithium metal counter electrode at an approximate current density of 0.02 mA/cm2, between voltage limits of 3.00 and 4.20 V. The upper voltage limit was increased by 0.1 V on subsequent cycles. The testing was carried out at room temperature. It is shown that lithium ions are extracted from the active material during the initial charging of the cell. A charge equivalent to a material specific capacity of 130 mAh/g is extracted from the active material. The re-insertion process corresponds to 63 mAh/g and indicates the reversibility of the ion extraction-insertion processes. The generally symmetrical nature of the charge-discharge curves further indicates the excellent reversibility of the system. In addition, the level of voltage hysteresis (i.e. the voltage difference between the charge and discharge processes) is extremely small, indicating the excellent kinetics of the extraction-insertion reactions. This is an important property that is useful for producing a high rate active material.

Na3Ni1.5Mg0.5SbO6 Prepared according to Example 34C.



[0042] Referring to Figure 7B. The Cell #203016 shows the constant current cycling data for the Na3Ni1.5Mg0.5SbO6 active material (X0336) made following Example 34c in a Na-ion cell where it is coupled with a Hard Carbon (Carbotron® P/J) anode material. The electrolyte used a 0.5 M solution of NaClO4 in propylene carbonate. The constant current data were collected at an approximate current density of 0.05 mA/cm2 between voltage limits of 1.80 and 4.20 V.

[0043] To fully charge the cell the Na-ion cell was potentiostatically held at 4.2 V at the end of the constant current charging process. The testing was carried out at room temperature. It is shown that sodium ions are extracted from the cathode active material, Na3Ni1.5Mg0.5SbO6, and inserted into the Hard Carbon anode during the initial charging of the cell. During the subsequent discharge process, sodium ions are extracted from the Hard Carbon and re-inserted into the Na3Ni1.5Mg0.5SbO6 cathode active material. The first discharge process corresponds to a specific capacity for the cathode of 91 mAh/g, indicating the reversibility of the sodium ion extraction-insertion processes. The generally symmetrical nature of the charge-discharge curves further indicates the excellent reversibility of the system. In addition, the level of voltage hysteresis (i.e. the voltage difference between the charge and discharge processes) is extremely small, indicating the excellent kinetics of the extraction-insertion reactions. This is an important property that is useful for producing a high rate active material.

Li3Ni1.5Mg0.5SbO6 Prepared according to Example 17. (comparative)



[0044] Referring to Figure 8B. The Cell #203018 shows the constant current cycling data for the Li3Ni1.5Mg0.5SbO6 active material (X0368) made according to Example 17 in a Li-ion cell where it is coupled with a crystalline graphite (supplied by Conoco Inc.) anode material. The electrolyte used a 1.0 M solution of LiPF6 in ethylene carbonate (EC) and diethyl carbonate (DEC). The constant current data were collected at an approximate current density of 0.05 mA/cm2 between voltage limits of 1.80 and 4.20 V. To fully charge the cell the Li-ion cell was potentiostatically held at 4.2 V at the end of the constant current charging process. The testing was carried out at room temperature. It is shown that lithium ions are extracted from the cathode active material, Li3Ni1.5Mg0.5SbO6, and inserted into the Graphite anode during the initial charging of the cell. During the subsequent discharge process, lithium ions are extracted from the crystalline graphite and re-inserted into the Li3Ni1.5Mg0.5SbO6 cathode active material. The first discharge process corresponds to a specific capacity for the cathode of 85 mAh/g, indicating the reversibility of the lithium ion extraction-insertion processes. The generally symmetrical nature of the charge-discharge curves further indicates the excellent reversibility of the system. In addition, the level of voltage hysteresis (i.e. the voltage difference between the charge and discharge processes) is extremely small, indicating the excellent kinetics of the extraction-insertion reactions. This is an important property that is useful for producing a high rate active material.

Na3Ni1.75Zn0.25SbO6 Prepared According to Example 35.



[0045] Figure 9B (Cell#203054) shows the long term constant current cycling performance (cathode specific capacity versus cycle number) of a Na-ion Cell comprising Carbotron® (Kureha Inc.) Hard Carbon // Na3Ni1.75Zn0.25SbO6 (Material = X0392) using a 0.5 M NaClO4 - propylene carbonate (PC) electrolyte. The constant current cycling test was carried out at 25 °C between voltage limits of 1.8 and 4.2 V. To fully charge the cell, the Na-ion cell was held at a cell voltage of 4.2 V at the end of the constant current charging process until the cell current had decayed to one tenth of the constant current value. During the charging of the cell, sodium ions are extracted from the cathode active material, and inserted into the Hard Carbon anode. During the subsequent discharge process, sodium ions are extracted from the Hard Carbon and re-inserted into the cathode active material. The initial cathode specific capacity (cycle 1) is 70 mAh/g. The Na-ion cell cycles more than 50 times with low capacity fade.

Na3Ni1.75Cu0.25SbO6 Prepared According to Example 36.



[0046] Figure 10B (Cell#203055) shows the long term constant current cycling performance (cathode specific capacity versus cycle number) of a Na-ion Cell comprising: Hard Carbon // Na3Ni1.75Cu0.25SbO6 (Material = X0393) using a 0.5 M NaClO4 - propylene carbonate (PC) electrolyte. The constant current cycling test was carried out at 25 °C between voltage limits of 1.8 and 4.2 V. To fully charge the cell, the Na-ion cell was held at a cell voltage of 4.2 V at the end of the constant current charging process until the cell current had decayed to one tenth of the constant current value. During the charging of the cell, sodium ions are extracted from the cathode active material, and inserted into the Hard Carbon anode. During the subsequent discharge process, sodium ions are extracted from the Hard Carbon and re-inserted into the cathode active material. The initial cathode specific capacity (cycle 1) is 62 mAh/g. The Na-ion cell cycles 18 times with low capacity fade.

Na3Ni1.25Mg0.75SbO6 Prepared According to Example 34d.



[0047] Figure 11B (Cell#203047) shows the long term constant current cycling performance (cathode specific capacity versus cycle number) of a Na-ion Cell comprising: Hard Carbon // Na3Ni1.25Mg0.75SbO6 (Material = X0373) using a 0.5 M NaClO4 - propylene carbonate (PC) electrolyte. The constant current cycling test was carried out at 25 °C between voltage limits of 1.8 and 4.0 V. To fully charge the cell, the Na-ion cell was held at a cell voltage of 4.0 V at the end of the constant current charging process until the cell current had decayed to one tenth of the constant current value. During the charging of the cell, sodium ions are extracted from the cathode active material, and inserted into the Hard Carbon anode.

[0048] During the subsequent discharge process, sodium ions are extracted from the Hard Carbon and re-inserted into the cathode active material. The initial cathode specific capacity (cycle 1) is 83 mAh/g. The Na-ion cell cycles more than 40 times with low capacity fade.

Na3Ni1.50Mn0.50SbO6 Prepared According to Example 37.



[0049] Figure 12B (Cell#203029) shows the long term constant current cycling performance (cathode specific capacity versus cycle number) of a Na-ion Cell comprising: Hard Carbon // Na3Ni1.50Mn0.50SbO6 (Material = X0380) using a 0.5 M NaClO4 - propylene carbonate (PC) electrolyte. The constant current cycling test was carried out at 25°C between voltage limits of 1.8 and 4.2 V. To fully charge the cell, the Na-ion cell was held at a cell voltage of 4.2 V at the end of the constant current charging process until the cell current had decayed to one tenth of the constant current value. During the charging of the cell, sodium ions are extracted from the cathode active material, and inserted into the Hard Carbon anode. During the subsequent discharge process, sodium ions are extracted from the Hard Carbon and re-inserted into the cathode active material. The initial cathode specific capacity (cycle 1) is 78 mAh/g. The Na-ion cell cycles 13 times with low capacity fade.

Li4FeSbO6 Prepared According to Example 38.



[0050] Figure 13B (Cell #303017) shows the constant current cycling data for the Li4FeSbO6 active material (X1120A). The electrolyte used a 1.0 M solution of LiPF6 in ethylene carbonate (EC) and diethyl carbonate (DEC). The constant current data were collected using a lithium metal counter electrode at an approximate current density of 0.04 mA/cm2 between voltage limits of 2.50 and 4.30 V. The testing was carried out at 25°C. It is shown that lithium ions are extracted from the active material during the initial charging of the cell. A charge equivalent to a material specific capacity of 165 mAh/g is extracted from the active material. The re-insertion process corresponds to 100 mAh/g, indicating the reversibility of the ion extraction-insertion processes. The generally symmetrical nature of the charge-discharge curves further indicates the excellent reversibility of the system.

Li4NiTeO6 Prepared According to Example 39



[0051] Figure 14B (Cell #303018) shows the constant current cycling data for the Li4NiTeO6 active material (X1121). The electrolyte used a 1.0 M solution of LiPF6 in ethylene carbonate (EC) and diethyl carbonate (DEC). The constant current data were collected using a lithium metal counter electrode at an approximate current density of 0.04 mA/cm2 between voltage limits of 2.50 and 4.40 V. The testing was carried out at 25°C. It is shown that lithium ions are extracted from the active material during the initial charging of the cell. A charge equivalent to a material specific capacity of 168 mAh/g is extracted from the active material. The re-insertion process corresponds to 110 mAh/g, indicating the reversibility of the alkali ion extraction-insertion processes. The generally symmetrical nature of the charge-discharge curves further indicates the excellent reversibility of the system.

Na4NiTeO6 Prepared According to Example 40.



[0052] Figure 15B (Cell #303019) shows the constant current cycling data for the Na4NiTeO6 active material (X1122). The electrolyte used a 1.0 M solution of LiPF6 in ethylene carbonate (EC) and diethyl carbonate (DEC). The constant current data were collected using a lithium metal counter electrode at an approximate current density of 0.04 mA/cm2 between voltage limits of 2.50 and 4.30 V. The testing was carried out at 25°C. It is shown that sodium ions are extracted from the active material during the initial charging of the cell. A charge equivalent to a material specific capacity of 75 mAh/g is extracted from the active material. The re-insertion process corresponds to 30 mAh/g, indicating the reversibility of the alkali ion extraction-insertion processes. The generally symmetrical nature of the charge-discharge curves further indicates the excellent reversibility of the system.


Claims

1. A sodium-ion cell comprising a cathode electrode containing an active material of the formula:

        AaMbXxOy

wherein

A is selected from sodium, or a mixture of sodium and potassium, or a mixture of sodium and lithium;

M is selected from one or more transition metals and/or one or more non-transition metals and/or one or more metalloids;

X comprises one or more atoms selected from niobium, antimony, tellurium, tantalum, bismuth and selenium;

wherein
0<a ≤ 6; b is in the range: 0 < b ≤4; x is in the range 0 < x ≤1 and y is in the range 2 ≤y ≤10
and further wherein
M comprises one or more transition metals and/or one or more non-transition metals and/or one or more metalloids selected from titanium, vanadium, chromium, molybdenum, tungsten, manganese, iron, osmium, cobalt, nickel, palladium, platinum, copper, silver, gold, zinc, cadmium, magnesium, calcium, beryllium, strontium, barium, aluminium and boron.
 
2. A sodium-ion cell comprising a cathode electrode containing an active material according to claim 1 wherein at least one of the one or more transition metals has an oxidation state of +2 and at least one of the one or more non-transition metals has an oxidation state of + 2.
 
3. A sodium-ion cell comprising a cathode electrode containing an active material according to claim 1 wherein at least one of the one or more transition metals has an oxidation state of either +2 or +3 and wherein at least one of the one or more non-transition metals has an oxidation state of +3.
 
4. A sodium-ion cell comprising a cathode electrode containing an active material according to claim 1 wherein M is selected from one or more of copper, nickel, cobalt, manganese, aluminium, vanadium, magnesium and iron.
 
5. A sodium-ion cell comprising a cathode electrode containing an active material according to claim 1 of the formula: AaMbSbxOy, wherein A is selected from sodium, or a mixture of sodium and potassium, or a mixture of sodium and lithium, and M is one or more metals selected from cobalt, nickel, manganese, iron, copper, aluminium, vanadium and magnesium.
 
6. A sodium-ion cell comprising a cathode electrode containing an active material according to claim 1 of the formula: AaMbTexOy, wherein A is selected from sodium, or a mixture of sodium and potassium, or a mixture of sodium and lithium, and M is one or more metals selected from cobalt, nickel, manganese, iron, copper, aluminium, vanadium and magnesium.
 
7. A sodium-ion cell comprising a cathode electrode containing an active material according to claim 5 or 6 wherein a is in the range 0< a ≤ 5; b is in the range 0 ≤ b ≤ 3; x is in the range 0.5 ≤ x ≤ 1; and y is in the range 2≤ y ≤ 9.
 
8. A sodium-ion cell comprising a cathode electrode according to any of claims 1 to 7 containing one or more active materials selected from: Na3Ni2SbO6, Na3Ni1.5Mg0.5SbO6, Na3Co2SbO6, Na3Co1.5Mg0.5SbO6, Na3Mn2SbO6, Na3Fe2SbO6, Na3Cu2SbO6, Na2AlMnSbO6, Na2AlNiSbO6, Na2VMgSbO6, NaCoSbO4, NaNiSbO4, NaMnSbO4, Na4FeSbO6, Na0.8Co0.6Sb0.4O2, Na0.8Ni0.6Sb0.4O4, Na2Ni2TeO6, Na2Co2TeO6, Na2Mn2TeO6, Na2Fe2TeO6, Na3Ni2-zMgzSbO6 (0 ≤ z ≤ 0.75), Na4NiTeO6, Na2NiSbO5, Na4Fe3SbO9, Na2Fe3SbO8, Na5NiSbO6, Na4MnSbO6, Na3MnTeO6, Na3FeTeO6, Na4Fe1-z(Ni0.5Ti0.5)zSbO6 (0 ≤ z ≤ 1), Na4Fe0.5Ni0.25Ti0.25SbO6, Na4Fe1-z(Ni0.5Mn0.5)zSbO6 (0 ≤ z ≤ 1), Na4Fe0.5Ni0.25Mn0.25SbO6, Na5-zNi1-zFezSbO6 (0 ≤ z ≤ 1), Na4.5Ni0.5Fe0.5SbO6, Na3Ni1.75Zn0.25SbO6, Na3Ni1.75Cu0.25SbO6 and Na3Ni1.50Mn0.50SbO6.
 
9. A sodium-ion cell according to claim 1 further comprising a counter electrode and one or more electrolyte materials.
 
10. A sodium-ion cell according to claim 9 wherein the electrolyte material comprises one or more selected from an aqueous electrolyte material and a non-aqueous electrolyte material.
 
11. An energy storage device comprising a sodium-ion cell according to any of claims 1 to 10.
 
12. A rechargeable battery comprising a sodium-ion cell according to any of claims 1 to 10.
 
13. An electrochemical device comprising a sodium-ion cell according to any of claims 1 to 10.
 
14. An electrochromic device comprising a sodium-ion cell according to any of claims 1 to 10.
 


Ansprüche

1. Natriumionenzelle, die eine Kathodenelektrode umfasst, die ein aktives Material der Formel:

        AaMbXxOy

enthält, wobei

A unter Natrium oder einer Mischung von Natrium und Kalium oder einer Mischung von Natrium und Lithium ausgewählt ist;

M unter einem oder mehreren Übergangsmetallen und/oder einem oder mehreren Nichtübergangsmetallen und/oder einem oder mehreren Metalloiden ausgewählt ist;

X ein oder mehrere Atome umfasst ausgewählt unter Niob, Antimon, Tellur, Tantal, Wismut und Selen;

wobei
0<a ≤ 6; b im Bereich von: 0 < b ≤4 liegt; x im Bereich von 0 < x ≤1 liegt und y im Bereich von 2 ≤y ≤10 liegt
und wobei ferner
M ein oder mehrere Übergangsmetalle und/oder ein oder mehrere Nichtübergangsmetalle und/oder ein oder mehrere Metalloide umfasst ausgewählt unter Titan, Vanadium, Chrom, Molybdän, Wolfram, Mangan, Eisen, Osmium, Kobalt, Nickel, Palladium, Platin, Kupfer, Silber, Gold, Zink, Cadmium, Magnesium, Calcium, Beryll, Strontium, Barium, Aluminium und Bor.
 
2. Natriumionenzelle, die eine Kathodenelektrode umfasst, die ein aktives Material nach Anspruch 1 enthält, wobei mindestens eines des einen oder der mehreren Übergangsmetalle einen Oxidationszustand von +2 aufweist und mindestens eines des einen oder der mehreren Nichtübergangsmetalle einen Oxidationszustand von +2 aufweist.
 
3. Natriumionenzelle, die eine Kathodenelektrode umfasst, die ein aktives Material nach Anspruch 1 enthält, wobei mindestens eines des einen oder der mehreren Übergangsmetalle einen Oxidationszustand von entweder +2 oder +3 aufweist und wobei mindestens eines des einen oder der mehreren Übergangsmetalle einen Oxidationszustand von +3 aufweist.
 
4. Natriumionenzelle, die eine Kathodenelektrode umfasst, die ein aktives Material nach Anspruch 1 enthält, wobei M unter einem oder mehreren von Kupfer, Nickel, Kobalt, Mangan, Aluminium, Vanadium, Magnesium und Eisen ausgewählt ist.
 
5. Natriumionenzelle, die eine Kathodenelektrode umfasst, die ein aktives Material nach Anspruch 1 der Formel: AaMbSbxOy enthält, wobei A unter Natrium oder einer Mischung von Natrium und Kalium oder einer Mischung von Natrium und Lithium ausgewählt ist und M ein oder mehrere Metalle ist ausgewählt unter Kobalt, Nickel, Mangan, Eisen, Kupfer, Aluminium, Vanadium und Magnesium.
 
6. Natriumionenzelle, die eine Kathodenelektrode umfasst, die ein aktives Material nach Anspruch 1 der Formel: AaMbTexOy enthält, wobei A unter Natrium oder einer Mischung von Natrium und Kalium oder einer Mischung von Natrium und Lithium ausgewählt ist und M ein oder mehrere Metalle ist ausgewählt unter Kobalt, Nickel, Mangan, Eisen, Kupfer, Aluminium, Vanadium und Magnesium.
 
7. Natriumionenzelle, die eine Kathodenelektrode umfasst, die ein aktives Material nach Anspruch 5 oder 6 enthält, wobei a im Bereich von 0< a ≤ 5 liegt; b im Bereich von 0 ≤ b ≤ 3 liegt; x im Bereich von 0,5 ≤ x ≤ 1 liegt; und y im Bereich von 2≤ y ≤ 9 liegt.
 
8. Natriumionenzelle, die eine Kathodenelektrode nach irgendeinem der Ansprüche 1 bis 7 umfasst, die ein oder mehrere aktive Materialien enthält, ausgewählt unter: Na3Ni2SbO6, Na3Ni1.5Mg0.5SbO6, Na3Co2SbO6, Na3Co1.5Mg0.5SbO6, Na3Mn2SbO6, Na3Fe2SbO6, Na3Cu2SbO6, Na2AlMnSbO6, Na2AlNiSbO6, Na2VMgSbO6, NaCoSbO4, NaNiSbO4, NaMnSbO4, Na4FeSbO6, Na0.8Co0.6Sb0.4O2, Na0.8Ni0.6Sb0.4O4, Na2Ni2TeO6, Na2Co2TeO6, Na2Mn2TeO6, Na2Fe2TeO6, Na3Ni2-zMgzSbO6 (0 ≤ z ≤ 0.75), Na4NiTeO6, Na2NiSbO5, Na4Fe3SbO9, Na2Fe3SbO8, Na5NiSbO6, Na4MnSbO6, Na3MnTeO6, Na3FeTeO6, Na4Fe1-z(Ni0.5Ti0.5)zSbO6 (0 ≤ z ≤ 1), Na4Fe0.5Ni0.25Ti0.25SbO6, Na4Fe1-z(Ni0.5Mn0.5)zSbO6 (0 ≤ z ≤ 1), Na4Fe0.5Ni0.25Mn0.25SbO6, Na5-zNi1-zFezSbO6 (0 ≤ z ≤ 1), Na4.5Ni0.5Fe0.5SbO6, Na3Ni1.75Zn0.25SbO6, Na3Ni1.75Cu0.25SbO6 und Na3Ni1.50Mn0.50SbO6.
 
9. Natriumionenzelle nach Anspruch 1, die ferner eine Gegenelektrode und ein oder mehrere Elektrolytmaterialien umfasst.
 
10. Natriumionenzelle nach Anspruch 9, wobei das Elektrolytmaterial eines oder mehrere umfasst ausgewählt unter einem wässrigen Elektrolytmaterial und einem nichtwässrigen Elektrolytmaterial.
 
11. Energiespeichervorrichtung, die eine Natriumionenzelle nach einem der Ansprüche 1 bis 10 umfasst.
 
12. Aufladbare Batterie, die eine Natriumionenzelle nach einem der Ansprüche 1 bis 10 umfasst.
 
13. Elektrochemische Vorrichtung, die eine Natriumionenzelle nach einem der Ansprüche 1 bis 10 umfasst.
 
14. Elektrochromvorrichtung, die eine Natriumionenzelle nach einem der Ansprüche 1 bis 10 umfasst.
 


Revendications

1. Pile à ion sodium comprenant une électrode cathode contenant un matériau actif de formule :

        AaMbXxOy

dans laquelle

A est choisi parmi le sodium, ou un mélange de sodium et de potassium, ou un mélange de sodium et de lithium ;

M est choisi parmi un ou plusieurs métaux de transition et/ou un ou plusieurs métaux de non-transition et/ou un ou plusieurs métalloïdes ;

X comprend un ou plusieurs atomes choisis parmi le niobium, l'antimoine, le tellure, le tantale, le bismuth et le sélénium ;

dans laquelle
0 < a ≤ 6 ; b est dans la plage : 0 < b ≤ 4 ; x est dans la plage 0 < x ≤ 1 et y est dans la plage 2 ≤ y ≤ 10
et en outre dans laquelle
M comprend un ou plusieurs métaux de transition et/ou un ou plusieurs métaux de non-transition et/ou un ou plusieurs métalloïdes choisis parmi le titane, le vanadium, le chrome, le molybdène, le tungstène, le manganèse, le fer, l'osmium, le cobalt, le nickel, le palladium, le platine, le cuivre, l'argent, l'or, le zinc, le cadmium, le magnésium, le calcium, le béryllium, le strontium, le baryum, l'aluminium et le bore.
 
2. Pile à ion sodium comprenant une électrode cathode contenant un matériau actif selon la revendication 1, dans laquelle au moins l'un des un ou plusieurs métaux de transition a un état d'oxydation de +2 et au moins l'un des un ou plusieurs métaux de non-transition a un état d'oxydation de +2.
 
3. Pile à ion sodium comprenant une électrode cathode contenant un matériau actif selon la revendication 1, dans laquelle au moins l'un des un ou plusieurs métaux de transition a un état d'oxydation de +2 ou +3 et dans laquelle au moins l'un des un ou plusieurs métaux de non-transition a un état d'oxydation de +3.
 
4. Pile à ion sodium comprenant une électrode cathode contenant un matériau actif selon la revendication 1, dans laquelle M est choisi parmi un ou plusieurs parmi le cuivre, le nickel, le cobalt, le manganèse, l'aluminium, le vanadium, le magnésium et le fer.
 
5. Pile à ion sodium comprenant une électrode cathode contenant un matériau actif selon la revendication 1 de formule : AaMbSbxOy, dans laquelle A est choisi parmi le sodium, ou un mélange de sodium et de potassium, ou un mélange de sodium et de lithium, et M est un ou plusieurs métaux choisis parmi le cobalt, le nickel, le manganèse, le fer, le cuivre, l'aluminium, le vanadium et le magnésium.
 
6. Pile à ion sodium comprenant une électrode cathode contenant un matériau actif selon la revendication 1 de formule : AaMbTexOy, dans laquelle A est choisi parmi le sodium, ou un mélange de sodium et de potassium, ou un mélange de sodium et de lithium, et M est un ou plusieurs métaux choisis parmi le cobalt, le nickel, le manganèse, le fer, le cuivre, l'aluminium, le vanadium et le magnésium.
 
7. Pile à ion sodium comprenant une électrode cathode contenant un matériau actif selon la revendication 5 ou 6, dans laquelle a est dans la plage 0 < a ≤ 5 ; b est dans la plage 0 ≤ b ≤ 3 ; x est dans la plage 0,5 ≤ x ≤ 1 ; et y est dans la plage 2 ≤ y ≤ 9.
 
8. Pile à ion sodium comprenant une électrode cathode selon l'une quelconque des revendications 1 à 7, contenant un ou plusieurs matériaux actifs choisis parmi : Na3Ni2SbO6, Na3Ni1,5Mg0,5SbO6, Na3Co2SbO6, Na3Co1,5Mg0,5SbO6, Na3Mn2SbO6, Na3Fe2SbO6, Na3Cu2SbO6, Na2AlMnSbO6, Na2AlNiSbO6, Na2VMgSbO6, NaCoSbO4, NaNiSbO4, NaMnSbO4, Na4FeSbO6, Na0,8Co0,6,Sb0,4O2, Na0,8Ni0,6Sb0,4O4, Na2Ni2TeO6, Na2Co2TeO6, Na2Mn2TeO6, Na2Fe2TeO6, Na3Ni2-zMgzSbO6, (0 ≤ z ≤ 0,75), Na4NiTeO6, Na2NiSbO5, Na4Fe3SbO9, Na2Fe3SbO8, Na5NiSbO6, Na4MnSbO6, Na3MnTeO6, Na3FeTeO6, Na4Fe1-z(Ni0,5Ti0,5)zSbO6 (0 ≤ z ≤ 1), Na4Fe0,5Ni0,25Ti0,25SbO6, Na4Fe1-z(Ni0,5Mn0,5)zSbO6, (0 ≤ z ≤ 1), Na4Fe0,5Ni0,25Mn0,25SbO6, Na5-zNi1-zFezSbO6 (0 ≤ z ≤ 1), Na4,5Ni0,5Fe0,5SbO6, Na3Ni1,75Zn0,25SbO6, Na3Ni1,75Cu0,25SbO6 et Na3Ni1,50Mn0,50SbO6.
 
9. Pile à ion sodium selon la revendication 1, comprenant en outre une contre-électrode et un ou plusieurs matériaux d'électrolyte.
 
10. Pile à ion sodium selon la revendication 9, dans laquelle le matériau d'électrolyte comprend un ou plusieurs éléments choisis parmi un matériau d'électrolyte aqueux et un matériau d'électrolyte non aqueux.
 
11. Dispositif de stockage d'énergie comprenant une pile à ion sodium selon l'une quelconque des revendications 1 à 10.
 
12. Batterie rechargeable comprenant une pile à ion sodium selon l'une quelconque des revendications 1 à 10.
 
13. Dispositif électrochimique comprenant une pile à ion sodium selon l'une quelconque des revendications 1 à 10.
 
14. Dispositif électrochromique comprenant une pile à ion sodium selon l'une quelconque des revendications 1 à 10.
 




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