EP3977542A1 - Matériaux d'électrode comprenant un oxyde lamellaire de potassium et de métal, électrodes les comprenant et leur utilisation en électrochimie - Google Patents
Matériaux d'électrode comprenant un oxyde lamellaire de potassium et de métal, électrodes les comprenant et leur utilisation en électrochimieInfo
- Publication number
- EP3977542A1 EP3977542A1 EP20812764.7A EP20812764A EP3977542A1 EP 3977542 A1 EP3977542 A1 EP 3977542A1 EP 20812764 A EP20812764 A EP 20812764A EP 3977542 A1 EP3977542 A1 EP 3977542A1
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- EP
- European Patent Office
- Prior art keywords
- potassium
- lithium
- electrode material
- metal
- material according
- 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.)
- Pending
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- H01M4/36—Selection of substances as active materials, active masses, active liquids
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- C01G45/00—Compounds of manganese
- C01G45/12—Manganates manganites or permanganates
- C01G45/1221—Manganates or manganites with a manganese oxidation state of Mn(III), Mn(IV) or mixtures thereof
- C01G45/1228—Manganates or manganites with a manganese oxidation state of Mn(III), Mn(IV) or mixtures thereof of the type [MnO2]n-, e.g. LiMnO2, Li[MxMn1-x]O2
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- C01G53/50—Nickelates containing alkali metals, e.g. LiNiO2 containing manganese of the type [MnO2]n-, e.g. Li(NixMn1-x)O2, Li(MyNixMn1-x-y)O2
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Definitions
- the present application relates to the field of electrochemically active materials and their uses in electrochemical applications. More particularly, the present application generally relates to electrode materials comprising a lamellar oxide of potassium and of metal as an electrochemically active material, the electrodes comprising them, their manufacturing processes and their use in electrochemical cells.
- Solid-state batteries are an emerging solution for electric vehicle batteries or traction batteries for new generation electric cars. Compared to conventional lithium-ion batteries using liquid electrolytes, all-solid-state batteries can generally be manufactured at lower cost, and can exhibit improved lifespan, faster charge times, higher performance, and improved safety. .
- batteries comprising lithium or sodium metallic anodes have been revisited and improved to replace graphite anodes. in high energy density storage systems.
- lithium lithium cobalt dioxide U0O 2
- lithium nickel manganese manganese cobalt oxides NMC
- NMC lithium nickel manganese manganese cobalt oxides
- the present technology relates to an electrode material comprising an electrochemically active material, said electrochemically active material comprising a lamellar oxide of potassium and of a metal of formula K X MO 2 , in which x is a number such as 0 ⁇ x £ 0.7, and M is selected from Co, Mn, Fe, Ni, Ti, Cr, V, Cu, Zr, Sb, and a combination of at least two thereof.
- the electrochemically active material comprises a lamellar oxide of potassium and of a metal of formula K x M y Mn 1-y O 2 , in which x is as defined here, y is a number such as 0 £ y £ 1, 0, and M is selected from Co, Fe, Ni, Ti, Cr, V, Cu, Zr, Sb, and a combination of at least two thereof.
- the lamellar oxide of potassium metal has the formula K x Fe y Mn 1-y O 2 , where x and y are as defined herein.
- the lamellar oxide of potassium metal is of the formula K x Ni 0.5X Mn 1-0.5X O 2 , where x is as defined herein .
- the lamellar oxide of potassium metal is of the formula K x Ni 0.5X Mn 1-0.5X-y M y O 2 , wherein x is as defined herein, y is a number such as 0 £ y £ (1.0 - 0.5x), and M is selected from Co, Fe, Ti, Cr, V, Cu, Zr, Sb, and a combination of at least two of these this.
- the lamellar oxide of potassium metal has the formula K x Ni 0.5X Mni- 0.5X Ti y O 2 , where x and y are as defined herein.
- the lamellar oxide of potassium metal is selected from the group consisting of K 0.67 Ni 0.33 Mn 0.67 O 2 , K 0.6 Ni 0.3 MnojO 2 , K 0.5 Ni 0.25 Mn 0.75 O 2 , K 0.4 Ni 0.2 Mn 0.8 O 2 , K 0.4 Ni 0.2 Mn 0, 6 T ⁇ 0.2 O 2 , K 0 , 4 Ni 0.2 Mn 0.7 Ti 0.1 O 2 , K 0.4 Ni 0.2 Mn 0.75 Ti 0.08 O 2 , K 0.4 Fe 0.4 Mn 0, 6 O 2 , K 0.4 Ni 0.1 Mn 0.9 O 2 , K 0.4 MnO 2 , K 0.3 Ni 0.1 5 Mn 0.85 O 2 , K 0.3 Ni 0.2 Mn 0, 8 O 2 , K 0.3 MnO 2 , KO 2 Ni 0 1 Mn 0.9 O 2 , K 0.2 Ni 0.2 Mn 0.8 O 2 , K 0.2 MnO 2 , K 0.1 Ni 0.05 Mn 0.95
- the present technology relates to an electrode material comprising an electrochemically active material, said electrochemically active material comprising a lamellar oxide of potassium and of a metal of the formula Na z K x MO 2 , in which x is a number such that 0 ⁇ x £ 0.7, z is a number such that 0 ⁇ x £ 0.8, and M is selected from Co, Mn, Fe, Ni, Ti, Cr, V, Cu, Zr, Sb, and a combination of at least two of these.
- the electrochemically active material comprises a lamellar oxide of potassium and of metal of the formula Na z K x M y Mn 1-y O 2 , in which x and z are as defined here, y is a number such that 0 £ y £ 1.0, and M is selected from Co, Fe, Ni, Ti, Cr, V, Cu, Zr, Sb, and a combination of at least two thereof.
- the lamellar oxide of potassium metal is of the formula Na z K x NiyMn 1-y O 2 , in which x and z are as defined herein, and y is a number such as 0 £ y £ 1, 0.
- the layered oxide and potassium metal is selected from the group consisting of Na 0.7 Ni 0.4 4K 0.08 IMN 0.59 O 2, 0 Na, K 6 0.08 Ni 0.34 Mn 0.66 O 2 , Na 0.7 4K 0.08 Ni 0.2 Mn 0.8 O 2 , Na 0.6 K 0.08 Ni 0.2 Mn 0.8 O 2 , Na 0.3 2K 0.08 Ni 0.2 Mn 0.8 O 2 , Na 0.2 K 0.2 Ni 0.2 Mn 0.8 O 2 , and a combination of at least two of these- this.
- the electrode material further comprises an electronically conductive material.
- the electronically conductive material is chosen from the group consisting of carbon black, acetylene black, graphite, graphene, carbon fibers, carbon nanofibers, carbon nanotubes, and a combination of at least two of these.
- the electrode material further comprises a binder.
- the binder is chosen from the group consisting of a polymer binder of polyether type, a fluoropolymer, and a water-soluble binder.
- the present technology relates to an electrode comprising an electrode material as defined herein on a current collector.
- the electrode is a positive electrode.
- the present technology relates to an electrochemical cell comprising a negative electrode, a positive electrode and an electrolyte, in which the positive electrode is as defined herein.
- the negative electrode comprises metallic lithium, metallic sodium, metallic potassium, or an alloy comprising at least one of these.
- the negative electrode comprises at least one of a pre-lithium alloy, pre-lithium graphite, pre-lithium silicon, pre-lithium oxide, or a combination of at least two thereof.
- the negative electrode comprises at least one of a presodized alloy, a presodized hard carbon, and a presodized oxide.
- the negative electrode comprises at least one of a prepotassed alloy, prepotassed graphite, prepotassed hard carbon, and prepotassed oxide.
- the electrolyte is a liquid electrolyte comprising a salt in a solvent.
- the electrolyte is a gel electrolyte comprising a salt in a solvent and optionally a solvating polymer.
- the electrolyte is a solid polymer electrolyte comprising a salt in a solvating polymer.
- the salt is selected from a lithium salt, a sodium salt, a potassium salt, and a combination of at least two thereof.
- the electrolyte is a glass or ceramic electrolyte.
- the electrolyte is a glass or ceramic electrolyte chosen from an electrolyte of the perovskite type deficient in sites, an electrolyte of the garnet type, a glass-ceramic electrolyte of the NASICON type, an electrolyte of the LISICON type, an aluminum oxide. (AI 2 O 3 ) conductor of sodium ion (Na + ) stabilized in lithium, and other similar glass or ceramic electrolytes.
- the present technology relates to a battery comprising at least one electrochemical cell as defined here.
- the battery is selected from the group consisting of a lithium battery, a lithium-ion battery, a sodium battery, a sodium-ion battery, a potassium battery , and a potassium-ion battery.
- FIGURES Figure 1 shows in (A) an X-ray diffraction pattern for a lamellar oxide powder of potassium metal of formula K 0.67 Ni 0.33 Mn 0.67 O 2 obtained using the solid state synthesis described in Example 1 (a); and in (B) an illustration of the crystal structure and characteristics of the crystal structure for the lamellar K 0.67 Ni 0.33 Mn 0.67 O 2 .
- Figure 2 shows in (A) an X-ray diffraction diagram for a powder of lamellar oxide of potassium and of metal of formula K 0.6 Ni 0.3 Mn 0.7 O 2 obtained using the synthesis in l solid state described in Example 1 (a); and in (B) an illustration of the crystal structure and characteristics of the crystal structure for the lamellar K 0.6 Ni 0.3 Mn 0.7 O 2 .
- Figure 3 shows in (A) an X-ray diffraction diagram for a powder of lamellar oxide of potassium and of metal of formula K 0.5 Ni 0.25 Mn 0.75 2 obtained using the synthesis in solid state described in Example 1 (a); and in (B) an illustration of the crystal structure and characteristics of the crystal structure for the K 0.5 Ni 0.25 Mn 0.75 2 lamellar.
- Figure 4 shows in (A) an X-ray diffraction diagram for a powder of lamellar oxide of potassium and of metal of formula K 0.4 Ni 0.2 Mn 0.8 O 2 obtained using the synthesis in l solid state described in Example 1 (a); and in (B) an illustration of the crystal structure and characteristics of the crystal structure for the K 0.4 Ni 0.2 Mn 0.8 O 2 lamellar.
- Figure 5 shows in (A) an X-ray diffraction pattern for a lamellar oxide powder of potassium metal of formula K 0.4 Ni 0.2 Mn 0.6 Ti 0.2 O 2 obtained using the solid state synthesis described in Example 1 (a); and in (B) two illustrations of the crystal structure for the lamellar K 0.4 Ni 0.2 Mn 0.6 Ti 0.2 O 2 .
- Figure 6 shows in (A) an X-ray diffraction pattern for a lamellar oxide powder of potassium metal of formula K 0.4 Ni 0.2 Mn 0.7 T ⁇ 0.1 O 2 obtained using the solid state synthesis described in Example 1 (a); and in (B) an illustration of the crystal structure and characteristics of the crystal structure for the K 0.4 Ni 0.2 Mn 0.7 Ti 0.1 O 2 lamellar.
- Figure 7 shows in (A) an X-ray diffraction pattern for a lamellar oxide powder of potassium metal of formula K 0.4 Ni 0.2 Mn 0.75 Ti 0.08 O 2 obtained using the solid state synthesis described in Example 1 (a); and in (B) an illustration of the crystal structure and characteristics of the crystal structure for the lamellar K 0.4 Ni 0.2 Mn 0.75 Ti 0.08 O 2 .
- Figure 8 shows in (A) an X-ray diffraction diagram for a lamellar oxide powder of potassium metal of formula K 0.4 Fe 0.4 Mn 0.6 O 2 obtained using the synthesis in solid state described in Example 1 (a); and in (B) an illustration of the crystal structure and characteristics of the crystal structure for the K 0.4 Fe 0.4 Mn 0.6 O 2 lamellar.
- Figure 9 shows in (A) an X-ray diffraction diagram for a lamellar oxide powder of potassium and metal of formula K 0.4 Ni 0.1 Mn 0.9 O 2 obtained using the synthesis in l solid state described in Example 1 (a); and in (B) and (C) an illustration of the crystal structure and characteristics of the crystal structure for the lamellar K 0.4 Ni 0.1 Mn 0.9 O 2 .
- Figure 10 shows in (A) an X-ray diffraction diagram for a lamellar oxide powder of potassium and metal of formula K 0.4 MnO 2 obtained using the solid state synthesis described in Example 1 (a); and in (B) an illustration of the crystal structure and characteristics of the crystal structure for the lamellar K 0.4 MnO 2 .
- Figure 1 1 shows in (A) an X-ray diffraction diagram for a powder of lamellar oxide of potassium and of metal of formula K 0.3 Ni 0.15 Mn 0.85 O 2 obtained using the synthesis in the solid state described in Example 1 (a); and in (B) an illustration of the crystal structure and characteristics of the crystal structure for the K 0.3 Ni 0.15 Mn 0.85 O 2 lamellar.
- Figure 12 shows in (A) an X-ray diffraction diagram for a lamellar oxide powder of potassium metal of formula K 0.3 Ni 0.2 Mn 0.8 O 2 obtained using the synthesis in solid state described in Example 1 (a); and in (B) an illustration of the crystal structure and characteristics of the crystal structure for the K 0.3 Ni 0.2 Mn 0.8 O 2 lamellar.
- Figure 13 shows in (A) an X-ray diffraction diagram for a lamellar oxide powder of potassium and metal of formula K 0.3 MnO 2 obtained using the solid state synthesis described in Example 1 (a); and in (B) an illustration of the crystal structure and characteristics of the crystal structure for the lamellar K 0.3 MnO 2 .
- Figure 14 shows in (A) an X-ray diffraction diagram for a lamellar oxide powder of potassium metal of formula K 0.2 Ni 0.1 Mn 0.9 O 2 obtained using the synthesis in the solid state described in Example 1 (a); and in (B) and (C) an illustration of the crystal structure and characteristics of the crystal structure for the K 0.2 Ni 0.1 Mn 0.9 O 2 lamellar.
- Figure 15 shows in (A) an X-ray diffraction diagram for a powder of lamellar oxide of potassium and of metal of the formula K 0.2 Ni 0.2 Mn 0.8 O 2 obtained using the synthesis in l solid state described in Example 1 (a); and in (B) an illustration of the crystal structure and characteristics of the crystal structure for the K 0.2 Ni 0.2 Mn 0.8 O 2 lamellar.
- Figure 16 shows in (A) an X-ray diffraction diagram for a lamellar oxide powder of potassium and metal of formula K 0.2 Mn 0.2 obtained using the solid state synthesis described in l Example 1 (a); and in (B) the characteristics of the crystal structure for the lamellar K 0.2 MnO 2 .
- Figure 17 shows in (A) an X-ray diffraction diagram for a lamellar oxide powder of potassium metal of formula K 0.1 Ni 0.08 Mn 0.95 O 2 obtained using the synthesis in solid state described in Example 1 (a); and in (B) an illustration of the crystal structure and characteristics of the crystal structure for the lamellar K 0.1 Ni 0.08 Mn 0.95 O 2 .
- Figure 18 shows in the X-ray diffraction diagrams for powders of lamellar oxides of potassium and metal of the formulas Na 0.74 K 0.08 Ni 0.4i Mn 0.59 O 2 (black line), Na 0, 6 K 0.08 Ni 0.3 4Mn 0.66 O 2 (red line), Na 0.74 K 0.08 Ni 0.2 Mn 0.8 O 2 (blue line), Na 0, eK 0 , 08 Ni 0.2 Mn 0.8 O 2 (pink line), Na 0.32 K 0, o 8 Ni 0.2 Mn 0.8 O 2 (burgundy line), and Na 0.2 K 0.2 Ni 0.2 Mn 0.8 O 2 (orange line) obtained using the solid state synthesis described in Example 1 (a).
- Figure 19 is a graph of the capacity (mAh.g -1 ) as a function of x for a lamellar oxide of potassium and metal of the formula K x Ni 0.5 xMn 1-0.5 xO 2 (where, x is a number such as 0.1 £ x £ 0.7), as described in Example 3 (b).
- the results are presented for a lithium-ion battery (red line) and for a sodium-ion battery (black line).
- Figure 20 shows in (A) two charge and discharge profiles for Cell 1 recorded at a cycling rate of 0.1 C between 1.5 V and 4.5 V vs Li + / Li; and in (B) two charge and discharge profiles for Cell 2 recorded at a cycling rate of 0.1 C between 1.5 V and 4.2 V vs Na + / Na, as described in Example 3 (b). Results are presented for a first (black line, 1) and a second (red line, 2) cycle of discharge and charge.
- Figure 21 shows in (A) two charge and discharge profiles for Cell 3 recorded at a cycling rate of 0.1 C between 1.5 V and 4.5 V vs Li + / Li; and in (B) two load profiles and discharge for Cell 4 recorded at a cycling rate of 0.1 C between 1.5 V and 4.2 V vs Na + / Na, as described in Example 3 (b). Results are presented for a first (black line, 1) and a second (red line, 2) cycle of discharge and charge.
- Figure 22 shows in (A) two charge and discharge profiles for Cell 5 recorded at a cycling rate of 0.1 C between 1.5 V and 4.5 V vs Li + / Li; and in (B) two charge and discharge profiles for Cell 6 recorded at a cycling rate of 0.1 C between 1.5 V and 4.2 V vs Na + / Na, as described in Example 3 (b). Results are presented for a first (black line, 1) and a second (red line, 2) cycle of discharge and charge.
- Figure 23 shows in (A) two charge and discharge profiles for Cell 7 recorded at a cycling rate of 0.1 C between 1.5 V and 4.5 V vs Li + / Li; and in (B) two charge and discharge profiles for Cell 8 recorded at a cycling rate of 0.1 C between 1.5 V and 4.2 V vs Na + / Na, as described in Example 3 (b). Results are presented for a first (black line, 1) and a second (red line, 2) cycle of discharge and charge.
- Figure 24 shows in (A) two charge and discharge profiles for Cell 9 recorded at a cycling rate of 0.1 C between 1.5 V and 4.5 V vs Li + / Li; and in (B) two charge and discharge profiles for Cell 10 recorded at a cycling rate of 0.1 C between 1.5 V and 4.2 V vs Na + / Na, as described in Example 3 (b). Results are presented for a first (black line, 1) and a second (red line, 2) cycle of discharge and charge.
- Figure 25 shows in (A) two charge and discharge profiles for Cell 11 recorded at a cycling speed of 0.1 C between 1.5 V and 4.5 V vs Li + / Li; and in (B) two charge and discharge profiles for Cell 12 recorded at a cycling speed of 0.1 C between 1.5 V and 4.2
- Figure 26 shows in (A) two charge and discharge profiles for Cell 13 recorded at a cycling rate of 0.1 C between 1.5 V and 4.5 V vs Li + / Li; and in (B) two charge and discharge profiles for Cell 14 recorded at a cycling speed of 0.1 C between 1.5 V and 4.2
- Figure 27 shows in (A) two charge and discharge profiles for Cell 15 recorded at a cycling rate of 0.1 C between 1.5 V and 4.5 V vs Li + / Li; and in (B) two load profiles and discharge for Cell 16 recorded at a cycling rate of 0.1 C between 1.5 V and 4.2
- Figure 28 shows in (A) two charge and discharge profiles for Cell 17 recorded at a cycling rate of 0.1 C between 1.5 V and 4.5 V vs Li + / Li; and in (B) two charge and discharge profiles for Cell 18 recorded at a cycling rate of 0.1 C between 1.5 V and 4.2
- Figure 29 shows in (A) two charge and discharge profiles for Cell 19 recorded at a cycling rate of 0.1 C between 1.5 V and 4.5 V vs Li + / Li; and in (B) two charge and discharge profiles for Cell 20 recorded at a cycling rate of 0.1 C between 1.5 V and 4.2
- Figure 30 shows in (A) two charge and discharge profiles for Cell 21 recorded at a cycling rate of 0.1 C between 1.5 V and 4.5 V vs Li + / Li; and in (B) two charge and discharge profiles for Cell 22 recorded at a cycling speed of 0.1 C between 1.5 V and 4.2
- Figure 31 shows in (A) two charge and discharge profiles for Cell 23 recorded at a cycling rate of 0.1 C between 1.5 V and 4.5 V vs Li + / Li; and in (B) two charge and discharge profiles for Cell 24 recorded at a cycling speed of 0.1 C between 1.5 V and 4.2
- Figure 32 shows in (A) two charge and discharge profiles for Cell 25 recorded at a cycling rate of 0.1 C between 1.5 V and 4.5 V vs Li + / Li; and in (B) two charge and discharge profiles for Cell 26 recorded at a cycling rate of 0.1 C between 1.5 V and 4.2
- Figure 33 shows in (A) two charge and discharge profiles for Cell 27 recorded at a cycling rate of 0.1 C between 1.5 V and 4.5 V vs Li + / Li; and in (B) two load profiles and discharge for Cell 28 recorded at a cycling rate of 0.1 C between 1.5 V and 4.2
- Figure 34 shows in (A) two charge and discharge profiles for Cell 29 recorded at a cycling rate of 0.1 C between 1.5 V and 4.5 V vs Li + / Li; and in (B) two charge and discharge profiles for Cell 30 recorded at a cycling rate of 0.1 C between 1.5 V and 4.2
- Figure 35 shows three charge and discharge profiles for Cell 33 recorded at a cycling rate of 0.1C between 1.5V and 4.2V vs Na + / Na, as described in Example 3 (b ). Results are presented for a first (black line, 1), second (red line, 2), and third (blue line, 3) cycle of discharge and charge.
- Figure 36 shows three charge and discharge profiles for Cell 34 recorded at a cycling rate of 0.1C between 1.5V and 4.2V vs Na + / Na, as described in Example 3 (b ). Results are presented for a first (black line, 1), second (red line, 2), and third (blue line, 3) cycle of discharge and charge.
- Figure 37 shows three charge and discharge profiles for Cell 35 recorded at a cycling rate of 0.1C between 1.5V and 4.2V vs Na + / Na, as described in Example 3 (b ). Results are presented for a first (black line, 1), second (red line, 2), and third (blue line, 3) cycle of discharge and charge.
- Figure 38 shows a graph of capacity (mAh.g ⁇ 1 ) and efficiency (%) as a function of the number of cycles recorded in (A) for Cells 1, 3, 5, 17, 19, 25 and 31 (lithium ion); and in (B) for Cells 2, 4, 6, 18, 26 and 32 (sodium-ion), as described in Example 3 (b).
- Figure 39 is a table of the reflection parameters of a metal lamellar oxide of potassium having the crystal structure characteristics shown in Table 1, as described in Example 2 (b).
- Figure 40 is a table of the reflection parameters of a metal lamellar oxide of potassium having the crystal structure characteristics shown in Table 2, as described in Example 2 (b).
- Figure 41 is a table of the reflection parameters of a lamellar oxide of potassium metal having the crystal structure characteristics shown in Table 3, as described in Example 2 (b).
- the present technology relates to electrode materials comprising a lamellar oxide of potassium and at least one metallic element as electrochemically active materials, their manufacturing processes and their use in electrochemical cells, for example, in lithium-ion batteries, sodium-ion batteries or potassium-ion batteries.
- the present technology relates to an electrode material including an electrochemically active material, in which said electrochemically active material includes a lamellar oxide of potassium and of a metal of formula K X MO 2 , in which x is a number such as 0 ⁇ x £ 0.7, and M is selected from Na, Li, Co, Mn, Fe, Ni, Ti, Cr, V, Cu, Zn, Mg, Zr, Sb, and a combination of at least two of those -this.
- the electrochemically active material includes a lamellar oxide of potassium and of a metal of formula K X MO 2 , in which x is a number such as 0 ⁇ x £ 0.7, and M is chosen from Co, Mn, Fe, Ni, Ti, Cr, V, Cu, Zr, Sb, and a combination of at least two of these.
- the electrochemically active material can include a lamellar oxide of potassium and of a metal of formula K x M y Mn 1-y O 2 , in which x is as defined here, y is a number such as 0 £ y £ 1, 0, and M is selected from Na, Li, Co, Fe, Ni, Ti, Cr, V, Cu, Zn, Mg, Zr, Sb, and a combination of at least two thereof.
- M can be chosen from Co, Fe, Ni, Ti, Cr, V, Cu, Zr, Sb, and a combination of at least two of these.
- the electrochemically active material may include a lamellar oxide of potassium and a metal of the formula K x Fe y Mn 1-y O 2 , in which y is as defined herein.
- the electrochemically active material can include a lamellar oxide of potassium and of metal of the formula K x Ni 0.5X Mn 1-0.5X O 2 , in which x is as defined here.
- the electrochemically active material may include a lamellar oxide of potassium and of metal of formula K x Ni 0.5X Mn 1-0.5X-y M y O 2 , in which x is as defined here, y is a number such that 0 £ y £ (1.0 - 0.5x), and M is selected from Na, Li, Co, Fe, Ti, Cr, V, Cu, Zn, Mg, Zr, Sb, and a combination of at least two of these. According to one example, M is chosen from Co, Fe, Ti, Cr, V, Cu, Zr, Sb, and a combination of at least two of these.
- the electrochemically active material may include a lamellar oxide of potassium and metal of the formula K x Ni 0.5X Mn 1-0.5X Ti y O 2 , wherein x and y are as defined herein.
- the electrochemically active material may include a lamellar oxide of potassium and a metal of the formula K 0.4 Ni 0.2 Mn 0.8-y Ti y O 2 , where y is a number such as 0 £ y £ 0.8.
- the electrochemically active material includes a lamellar oxide of potassium and of a metal of the formula Na z K x M02, in which x is as defined here, z is a number such that 0 ⁇ x £ 0.8, and M is selected from Li, Co, Mn, Fe, Ni, Ti, Cr, V, Cu, Zn, Mg, Zr, Sb, and a combination of at least two thereof.
- the electrochemically active material includes a lamellar oxide of potassium and of a metal of formula Na z K x MO 2 , in which x and z are as defined here, and M is chosen from Co, Mn, Fe, Ni, Ti, Cr, V, Cu, Zr, Sb, and a combination of at least two of these.
- the electrochemically active material can include a lamellar oxide of potassium and of metal of the formula Na z K x M y Mn 1-y O 2 , in which x and z are as defined here, y is a number such that 0 £ y £ 1, 0, and M is selected from Li, Co, Fe, Ni, Ti, Cr, V, Cu, Zn, Mg, Zr, Sb, and a combination of at least two of these this.
- M can be chosen from Co, Fe, Ni, Ti, Cr, V, Cu, Zr, Sb, and a combination of at least two of these.
- the electrochemically active material may include a lamellar oxide of potassium and a metal of the formula Na z K x Ni y Mn 1-y O 2 , wherein x, y and z are as defined herein.
- the electrochemically active material can include a lamellar oxide of potassium and metal of the formulas K x MnO 2 , K x NiMnO 2 , K x NiMnTiO 2 , or K x FeMnO 2 , where x is as shown here defined.
- Non-limiting examples of lamellar oxides of potassium and metal include K 0.67 Ni 0.33 Mn 0.67 O 2 , K 0.6 Ni 0.3 Mn 0.7 O 2 , K 0.5 Ni 0 , 2 5Mn 0.75 O 2 , K 0.4 Ni 0.2 Mn 0.8 O 2 , K 0.4 Ni 0.2 Mn 0, 6 T ⁇ 0.2 O 2 , K 0.4 Ni 0, 2 Mn 0.7 Ti 0.1 O 2, K 0.4 Ni 0.2 Mn 0.7 O 2 0.08 5Ti, K 0.4 Fe 0.4 Mn 0 6 O 2, K 0.4 Ni 0.1 Mn 0.9 O 2 , K 0.4 MnO 2 , K 0.3 Ni 0.15 Mn 0.8 5O 2 , K 0.3 Ni 0.2 Mn 0.8 O 2 , K 0 , 3 MnO 2 , K 0.2 Ni 0.1 Mn 0.9 O 2 , K 0.2 Ni 0.2 Mn 0.8 O 2 , K 0 MnO 2 , K 0.1 Ni 0.05 Mn 0.95 O 2
- the electrochemically active material can optionally be doped with other elements or impurities included in smaller amounts, for example to modulate or optimize its electrochemical properties.
- the electrochemically active material can be doped by the partial substitution of the metal by other ions.
- the electrochemically active material can be doped with a transition metal (e.g. Fe, Co, Ni, Mn, Ti, Cr, Cu, V, Zn, and / or Y) and / or a metal other than transition metal (eg, Mg, Al, and / or Sb).
- the electrode material can be substantially free of lithium and / or sodium.
- the electrochemically active material can include less than 2% by weight, less than 1% by weight, less than 0.5% by weight, less than 0.1% by weight, less than 0.05% by weight, or less than 0.01% by weight of lithium and / or sodium.
- the electrochemically active material can be delithiated and / or deodized.
- the electrochemically active material can be in the form of particles (eg, microparticles, or nanoparticles) which can be freshly formed and can further include a coating material.
- the coating material can be an electronically conductive material, for example, a carbon coating.
- the electrode material as described here may further include an electronically conductive material.
- Non-limiting examples of electronically conductive materials include a carbon source such as carbon black (eg, Ketjen TM carbon, or Super P TM carbon), acetylene black (eg, Shawinigan carbon, or Denka TM carbon black), graphite, graphene, carbon fibers (for example, gas-formed carbon fibers (VGCFs)), carbon nanofibers, carbon nanotubes (CNTs), or a combination of at least two of these.
- the electronically conductive material is chosen from Ketjen TM carbon, Super P TM carbon, VGCFs, and a combination of these.
- the electrode material as described here can also include a binder.
- the binder can be chosen for its compatibility with the different elements of an electrochemical cell. Any known compatible binder is contemplated.
- the binder can be a fluoropolymer binder, a water soluble (water soluble) binder, or an ion conductive polymer binder, such as copolymers composed of at least one lithium ion solvation segment. , such as a polyether, and optionally at least one crosslinkable segment (for example, polymers based on poly (ethylene oxide) (PEO) including methyl methacrylate units).
- PEO poly (ethylene oxide)
- the binder is a fluoropolymer such as polyvinylidene fluoride (PVDF) or polytetrafluoroethylene (PTFE).
- the binder is a water-soluble binder such as styrene-butadiene rubber (SBR), acrylonitrile-butadiene rubber (NBR), hydrogenated NBR (HNBR), epichlorohydrin rubber (CHR) , or acrylate rubber (ACM), and optionally comprising a thickening agent such as carboxymethylcellulose (CMC), or a polymer such as poly (acrylic acid) (PAA), poly (methyl methacrylate) (PMMA) , or a combination of these.
- SBR styrene-butadiene rubber
- NBR acrylonitrile-butadiene rubber
- HNBR hydrogenated NBR
- CHR epichlorohydrin rubber
- ACM acrylate rubber
- CMC carboxymethylcellulose
- PAA poly (acrylic acid)
- the binder is a polymer binder of polyether type.
- the polyether type polymeric binder is linear, branched and / or crosslinked and is based on PEO, poly (propylene oxide) (PPO), or a combination of both (such as an EO / PO copolymer), and optionally comprises crosslinkable units.
- the binder is PVDF, or a polymer of polyether type as defined here.
- the electrode material as described herein may further include additional components or additives such as inorganic particles, glass or ceramic particles, ionic conductors, salts, and the like.
- the present technology is also directed to an electrode including the electrode material as defined herein on a current collector (eg, aluminum foil or copper).
- a current collector eg, aluminum foil or copper
- the electrode can be self-supporting.
- the electrode is a positive electrode.
- the present technology also relates to an electrochemical cell including a negative electrode, a positive electrode and an electrolyte, in which the positive electrode is as defined herein.
- the negative electrode includes an electrochemically active material selected from all known compatible electrochemically active materials.
- the electrochemically active material of the negative electrode can be chosen for its electrochemical compatibility with the different elements of the electrochemical cell as defined here.
- Non-limiting examples of negative electrode electrochemically active materials include alkali metals, alkali metal alloys, pre-lithium electrochemically active materials, presodinated electrochemically active materials, and prepotched electrochemically active materials.
- the electrochemically active material of the negative electrode can be metallic lithium, metallic sodium, metallic potassium, or an alloy including at least one of these.
- the electrochemically active material of the negative electrode can be a pre-lithium alloy, a pre-lithium graphite, a pre-lithium silicon, a pre-lithium oxide, or a combination of these when compatible.
- the electrochemically active material of the negative electrode can be a presodized alloy, presodized hard carbon, or a presodized oxide.
- the electrochemically active material of the negative electrode can be a prepotassed alloy, a prepotassed graphite, a prepotassed hard carbon, or a prepotassed oxide.
- the electrolyte can also be chosen for its compatibility with the various elements of the electrochemical cell. Any type of compatible electrolyte is considered.
- the electrolyte can be a liquid electrolyte including a salt in a solvent.
- the electrolyte can be a gel electrolyte including a salt in a solvent and optionally a solvating polymer.
- the electrolyte can be a solid polymer electrolyte including a salt in a solvating polymer.
- the electrolyte can be a glass or ceramic electrolyte.
- the electrolyte is a solid polymer electrolyte free from solvent, a glass electrolyte, or a ceramic electrolyte.
- the salt if present in the electrolyte can be a metal salt, such as a lithium salt, a sodium salt, or a potassium salt.
- Non-limiting examples of lithium salts include lithium hexafluorophosphate (LiPF 6 ), lithium bis (trifluoromethanesulfonyl) imide (LiTFSI), lithium bis (fluorosulfonyl) imide (LiFSI), 2-trifluoromethyl-4, Lithium 5-dicyano- imidazolate (LiTDI), lithium 4,5-dicyano-1, 2,3-triazolate (LiDCTA), lithium bis (pentafluoroethylsulfonyl) imide (LiBETI), lithium tetrafluoroborate (L1BF 4 ), lithium bis (oxalato) borate (LiBOB), lithium nitrate (LiNO3), lithium chloride (LiCI), lithium bromide (LiBr), lithium fluoride (LiF), lithium perchlorate (LiCIO 4 ), lithium hexafluoroarsenate (LiAsF 6 ), lithium tri
- the lithium salt is LiPF 6 , LiFSI, LiTFSI, or LiTDI.
- sodium salts include sodium hexafluorophosphate (NaPF 6), sodium perchlorate (NaClO 4), bis (trifluoromethanesulfonyl) imide sodium (NaTFSI), bis (fluorosulfonyl) imide sodium (nafsi ), sodium 2-trifluoromethyl-4,5-dicyano-imidazolate (NaTDI), sodium bis (pentafluoroethylsulfonyl) imide (NaBETI), sodium trifluoromethanesulfonate (NaSO 3 CF 3 ) (NaTf), sodium fluoride (NaF), sodium nitrate (NaNO 3 ), and their combinations.
- the sodium salt is NaPF 6 , NaFSI, NaTFSI, or NaCIO 4 .
- potassium salts include potassium hexafluorophosphate (KPF 6 ), potassium bis (trifluoromethanesulfonyl) imide (KTFSI), potassium bis (fluorosulfonyl) imide (KFSI), potassium trifluoromethanesulfonate (KSO 3) CF 3 ) (KTf), and their combinations.
- the potassium salt is KPF 6 .
- the solvent if present in the electrolyte may be a non-aqueous solvent.
- non-aqueous solvents include cyclic carbonates such as ethylene carbonate (EC), propylene carbonate (PC), butylene carbonate (BC), and vinylene carbonate (VC); acyclic carbonates such as dimethyl carbonate (DMC), diethyl carbonate (DEC), methyl ethyl carbonate (EMC), and dipropyl carbonate (DPC); lactones such as ⁇ -butyrolactone (g-BL), and ⁇ -valerolactone (g-VL); acyclic ethers such as 1,2-dimethoxyethane (DME), 1, 2-diethoxyethane (DEE), ethoxy methoxy ethane (EME), trimethoxymethane, and ethylmonoglyme; cyclic ethers such as tetrahydrofuran, 2-methyltetrahydrofuran, 1, 3-
- the electrolyte comprises a salt chosen from lithium hexafluorophosphate (LiPF 6 ), sodium hexafluorophosphate (NaPF 6 ), sodium perchlorate (NaCIO 4 ), or potassium hexafluorophosphate (KPF 6) ) dissolved in a mixture of non-aqueous solvents such as a mixture of ethylene carbonate and diethyl carbonate (EC / DEC) ([3: 7] by volume), ethylene carbonate and dimethyl carbonate (EC / DMC) ([4: 6] by volume), or dissolved in dimethyl carbonate (DMC), or propylene carbonate.
- LiPF 6 lithium hexafluorophosphate
- NaPF 6 sodium hexafluorophosphate
- NaCIO 4 sodium perchlorate
- KPF 6 potassium hexafluorophosphate
- the electrolyte is a liquid electrolyte and the electrode material comprises an electrochemically active material, an electronically conductive material and a binder in a composition ratio of about 80: 10: 10.
- the material d The electrode comprises about 80% by weight of the electrochemically active material, about 10% by weight of the electronically conductive material and about 10% by weight of the binder.
- the electrolyte is a gel electrolyte or a polymer gel electrolyte.
- the polymer gel electrolyte can include, for example, a polymer precursor and a salt (eg, a salt as defined above), a solvent (eg, a solvent as defined above), and a polymerization initiator. and / or crosslinking, when necessary.
- Non-limiting examples of gel electrolytes include, without limitation, the gel electrolytes described in PCT patent applications published under numbers WO2009 / 111860 (Zaghib et al.) And WO2004 / 068610 (Zaghib et al.).
- the electrolyte can also be a solid polymer electrolyte.
- the solid polymer electrolyte can be chosen from all known solid polymer electrolytes and can be chosen for its compatibility with the various elements of the electrochemical cell.
- the solid polymer electrolyte can be chosen for its compatibility with lithium, sodium, and / or potassium.
- Solid polymer electrolytes generally comprise a salt as well as one or more solid polar polymer (s), optionally crosslinked.
- Polyether type polymers such as those based on PEO, can be used, but several other compatible polymers are also known for the preparation of solid polymer electrolytes and are also contemplated.
- the polymer can be crosslinked. Examples of such polymers include branched polymers, for example, star polymers or comb polymers such. than those described in the PCT patent application published under number W02003 / 063287 (Zaghib et al.).
- the electrolyte is a solid polymer electrolyte including a salt in a solvating polymer.
- the polymer of the solid polymer electrolyte is PEO and the salt is LiTFSI, LiFSI, LiTDI, NaTFSI, or NaFSI.
- the electrolyte is a solid polymer electrolyte and the electrode material comprises from about 50% by weight to about 75% by weight of the electrochemically active material, from about 1% by weight to about 5% by weight. weight of the electronically conductive material, and from about 20% by weight to about 49% by weight of the binder.
- the electrolyte is a ceramic electrolyte.
- the ceramic electrolyte may include an ion-conductive crystalline ceramic or an ion-conductive amorphous ceramic (eg, ion-conductive amorphous glass) or an ion-conductive glass ceramic.
- Non-limiting examples of glass or ceramic electrolytes include site-deficient perovskite-type electrolytes, garnet-type electrolytes, NASICON-type glass-ceramic electrolytes, LISICON-type electrolytes, aluminum oxides (AI 2 O 3 ) conductors of sodium ions (Na + ) stabilized with lithium, and other similar glass or ceramic electrolytes.
- a gel electrolyte or a liquid electrolyte as defined above can also impregnate a separator such as a polymer separator.
- separators include membranes of polyethylene (PE), polypropylene (PP), cellulose, polytetrafluoroethylene (PTFE), poly (vinylidene fluoride) (PVDF), and polypropylene-polyethylene-polypropylene (PP / PE / PP).
- the separator is a commercial polymer separator of the Celgard TM type.
- the electrolyte can also optionally comprise additional components or additives such as ionic conductors, inorganic particles, glass or ceramic particles, for example, nanoceramics (such as Al 2 O 3 , TiO 2 , SiO 2 , and other similar compounds) and other similar additives.
- additional components or additives such as ionic conductors, inorganic particles, glass or ceramic particles, for example, nanoceramics (such as Al 2 O 3 , TiO 2 , SiO 2 , and other similar compounds) and other similar additives.
- the present technology also relates to a battery comprising at least one electrochemical cell as defined here.
- the battery can be a lithium battery, a lithium-ion battery, a sodium battery, a sodium-ion battery, a potassium battery, or a potassium-ion battery.
- the battery is a lithium battery or a lithium-ion battery.
- the electrolyte is a liquid electrolyte as defined here and the electrochemically active material of the negative electrode comprises metallic lithium, a lithium-based alloy, a pre-lithium alloy, a pre-lithium graphite, a pre-lithium silicon, or a prelithiated oxide.
- the electrolyte is a gel electrolyte as defined here and the electrochemically active material of the negative electrode comprises metallic lithium, a lithium-based alloy, a pre-lithium alloy, a pre-lithium graphite, or a lithium-based alloy. pre-lithium silicon.
- the electrolyte is a solid polymer electrolyte and the electrochemically active material of the negative electrode comprises metallic lithium, a lithium-based alloy, a prithied graphite, or a prithied silicon.
- the electrolyte is a ceramic electrolyte and the electrochemically active material of the negative electrode comprises metallic lithium, a lithium-based alloy, or a preithied graphite, and / or a preithied silicon.
- the battery is a sodium battery or a sodium-ion battery.
- the electrolyte is a liquid electrolyte as defined here and the electrochemically active material of the negative electrode comprises metallic sodium, a sodium-based alloy, a presodium alloy, presodized hard carbon, or an oxide. presodied.
- the electrolyte is a gel electrolyte as defined herein and the electrochemically active material of the negative electrode comprises metallic sodium, a sodium-based alloy, a presodized alloy, or presodized hard carbon. .
- the electrolyte is a solid polymer electrolyte and the electrochemically active material of the negative electrode comprises metallic sodium, a sodium-based alloy, or presodized hard carbon.
- the electrolyte is a ceramic electrolyte and the electrochemically active material of the negative electrode comprises metallic sodium, a sodium-based alloy, or presodized hard carbon.
- the battery is a potassium battery or a potassium-ion battery.
- the electrolyte is a liquid electrolyte as defined here and the electrochemically active material of the negative electrode comprises metallic potassium, a potassium-based alloy, a pre-potassium alloy, a pre-potassium graphite, a pre-potassium hard carbon, or a pre-potassium oxide.
- the electrolyte is an electrolyte gel as defined herein and the electrochemically active material of the negative electrode comprises metallic potassium, a potassium-based alloy, a pre-potassium alloy, a pre-potassium graphite, or a pre-potassium hard carbon.
- the electrolyte is a solid polymer electrolyte and the electrochemically active material of the negative electrode comprises metallic potassium, a potassium-based alloy, a pre-potassium graphite, or a pre-potassium hard carbon.
- the electrolyte is a ceramic electrolyte and the electrochemically active material of the negative electrode comprises metallic potassium, a potassium-based alloy, a pre-potassium graphite, or a pre-potassium hard carbon.
- the present technology also relates to a lamellar oxide of potassium and of metal which is in crystalline form and of formula K X MO 2 , in which x is a number such as 0 ⁇ x £ 0.7, and M is chosen from Li, Co , Mn, Fe, Ni, Ti, Cr, V, Cu, Zn, Mg, Zr, Sb and their combinations.
- the present technology also relates to a lamellar oxide of potassium and of metal in crystalline form of formula K X MO 2 , in which x is a number such that 0 ⁇ x £ 0.7, and M is chosen from Co, Mn, Fe, Ni, Ti, Cr, V, Cu, Zr, Sb, and their combinations.
- the lamellar oxide of potassium metal in crystalline form is of formula K 0.67 Ni 0.33 Mn 0.67 O 2 , and has an XRD unit substantially as shown in Figure 1.
- the lamellar oxide of potassium and of metal in crystalline form is of formula K 0.6 Ni 0.3 Mn 0.7 O 2 , and has an XRD unit substantially as shown in Figure 2.
- the lamellar oxide of potassium and of metal in crystalline form is of formula K 0.5 Ni 0.25 Mn 075 O 2 , and has an XRD unit substantially as shown in Figure 3.
- the lamellar oxide of potassium and of metal in crystalline form is of formula K 0.4 Ni 0.2 Mn 0.8 O 2 , and has an XRD unit substantially as shown in Figure 4.
- the lamellar oxide of potassium and of metal in crystalline form is of formula K 0.4 Ni 0.2 Mn 0.6 Ti 0.2 O 2 , and has an XRD unit substantially as shown in Figure 5.
- the lamellar oxide of potassium and of metal in crystalline form is of formula K 0.4 Ni 0.2 Mn 0.7 Ti 0.1 O 2 , and has an XRD unit substantially as shown in Figure 6.
- the lamellar oxide of potassium and of metal in crystalline form is of formula K 0.4 Ni 0.2 Mn 0.75 Ti 0.08 O 2 , and has an XRD unit substantially as shown in Figure 7.
- the lamellar oxide of potassium and of metal in crystalline form is of formula K 0.4 Fe 0.4 Mn 0.6 O 2 , and has an XRD unit substantially as shown in Figure 8.
- the lamellar oxide of potassium and of metal in crystalline form is of formula K 0.4 Ni 0.1 Mn 0.9 O 2 , and has an XRD unit substantially as shown in Figure 9.
- the lamellar oxide of potassium and of metal in crystalline form is of formula K 0.4 MnO 2 , and has an XRD unit substantially as shown in Figure 10.
- the lamellar oxide of potassium and of metal in crystalline form is of formula K 0.5 Ni 0.15 Mn 0.85 O 2 , and has an XRD unit substantially as shown in Figure 11.
- the lamellar oxide of potassium and of metal in crystalline form is of formula K 0.3 Ni 0.2 Mn 0.8 O 2 , and has an XRD unit substantially as shown in Figure 12.
- the lamellar oxide of potassium and of metal in crystalline form is of formula K 0.3 MnO 2 , and has an XRD unit substantially as shown in Figure 13.
- the lamellar oxide of potassium and of metal in crystalline form is of formula K 0.2 Ni 0.1 Mn 0.9 O 2 , and has an XRD unit substantially as shown in Figure 14.
- the lamellar oxide of potassium and of metal in crystalline form is of formula K 0.2 Ni 0.2 Mn 0.8 O 2 , and has an XRD unit substantially as shown in Figure 15.
- the lamellar oxide of potassium and of metal in crystalline form is of formula K 0.2 MnO 2 , and has an XRD unit substantially as shown in Figure 16.
- the lamellar oxide of potassium and of metal in crystalline form is of formula K 0.1 Ni 0.08 Mn 0.95 O 2 , and has an XRD unit substantially as shown in Figure 17.
- the lamellar oxide of potassium and of metal in crystalline form is of formula Na 0.74 K 0.08 Ni 0.41 Mn 0.59 O 2 , Na 0.6 K 0.08 Ni 0, 3 4mn 0, 6 6O 2, Na 0.7 4K 0.08 Ni 0.2 Mn 0.8 O 2, Na 0, qK 0.08 Ni 0.2 Mn 0.8 O 2, Na 0.3 2K 0.08 Ni 0.2 Mn 0.8 O 2 , or Na 0.2 K 0.2 Ni 0.2 Mn 0.8 O 2 , and has an XRD pattern substantially as shown in Figure 18.
- the lamellar oxide of potassium and of metal in crystalline form of formula K X MO 2 has XRD 2Q (°) reflections substantially as presented in FIG. 39.
- the lamellar oxide of potassium and metal in crystalline form of formula K X MO 2 has XRD 2Q (°) reflections substantially as shown in Figure 40.
- the lamellar oxide of potassium and metal in crystalline form of formula K X MO 2 has XRD 2Q (°) reflections substantially as presented in Figure 41.
- the lamellar oxide of potassium and of metal in crystalline form is of formula K 0.4 Ni 0, 2 Mn 0.8 O 2 , and has an XRD motif substantially as shown in Figure 4, or has XRD 2Q (°) reflections substantially as shown in Figure 40.
- the lamellar oxide of potassium and of metal in crystalline form is of formula K 0.4 Ni 0.2 Mn 0.6 Ti 0.2 O 2 , and has an XRD unit substantially as shown. in Figure 5.
- the lamellar oxide of potassium and of metal in crystalline form is of formula K 0.4 Ni 0.2 Mn 0.7 Ti 0.1 O 2 , and has an XRD unit substantially as shown. in Figure 6, or has XRD 2Q (°) reflections substantially as shown in Figure 40.
- the lamellar oxide of potassium and of metal in crystalline form is of formula K 0.4 Ni 0.2 Mn 0.75 Ti 0.08 O 2 , and has an XRD unit substantially as shown. in Figure 7, or has XRD 2Q (°) reflections substantially as shown in Figure 40.
- the lamellar oxide of potassium and of metal in crystalline form is of formula K 0.4 Fe 0.4 Mn 0.6 O 2 , and has an XRD unit substantially as shown in Figure 8 , or has XRD 2Q (°) reflections substantially as presented in Figure 41.
- the lamellar oxide of potassium and metal in crystalline form is of formula K 0.4 Ni 0.1 Mn 0.9 O 2 , and has an XRD pattern substantially as shown in Figure 9, or has XRD 2Q (°) reflections substantially as shown in Figure 39 and / or Figure 40.
- the lamellar oxide of potassium and of metal in crystalline form is of formula K 0.5 Ni 0.15 Mn 0.85 O 2 , and has an XRD unit substantially as shown in Figure 11 , or has XRD 2q (°) reflections substantially as shown in Figure 40.
- the lamellar oxide of potassium and of metal in crystalline form is of formula K 0.3 Ni 0.2 Mn 0.8 O 2 , and has an XRD unit substantially as shown in Figure 12 , or has XRD 2Q (°) reflections substantially as shown in Figure 40.
- the lamellar oxide of potassium and of metal in crystalline form is of formula K 0.2 Ni 0.1 Mn 0.9 O 2 , and has an XRD unit substantially as shown in Figure 14 , or has XRD 2Q (°) reflections substantially as shown in Figure 40 and / or Figure 41.
- the lamellar oxide of potassium and of metal in crystalline form is of formula K 0.2 Ni 0.2 Mn 0.8 O 2 , and has an XRD unit substantially as presented in FIG. 15, or has XRD 2Q (°) reflections substantially as shown in Figure 41.
- the lamellar oxide of potassium and metal in crystalline form is of formula K 0.1 Ni 0, 08 Mn 0.95 O 2 , and has an XRD pattern substantially as shown in Figure 17, or has XRD 2Q (°) reflections substantially as shown in Figure 41.
- Na 0.3 2K 0.08 Ni 0.2 Mn 0.8 O 2 , and Na 0.2 K 0.2 Ni 0.2 Mn 0.8 O 2 were prepared using reaction techniques solid state.
- the respective precursors K2CO3 / KOH, and metal oxides such as Na 2 CO 3 , Mn 2 O 3 , C0 2 O 3 , CuO, ZrO 2 , NiO, Fe 2 0 3 , and TiO 2 ) were weighed in order to 'obtain the desired stoichiometries.
- the samples were prepared by grinding and mixing the precursor powders.
- the ground and mixed precursor powders were then placed in an oven and heated to a temperature between 600 ° C and 1000 ° C under an atmosphere of air or oxygen for 5 to 24 hours. For example, at a temperature between 800 ° C and 1000 ° C and for 6 to 8 hours.
- the lamellar oxides of potassium and of metal as defined herein can be prepared using techniques of synthesis in liquid medium.
- the lamellar oxides of potassium and metal as defined herein can be prepared by a sol-gel process, for example, by a sol-gel process (333SG) similar to that described by Hashem et al. (Hashem, Ahmed M., et al. Research on Engineering Structures and Materials 1.2 (2015): 81- 97).
- sol-gel powders 333SG are synthesized using citric acid as the chelating agent.
- the respective precursors (metal acetates, in which the metal is Na, Mn, Ti, K, Fe or Ni) are weighed to obtain the desired stoichiometry and dissolved in distilled water.
- the solution is added dropwise to an aqueous citric acid solution of about 1 mol / L stirred continuously.
- the pH is adjusted to a value between about 7.0 and about 8.0 with ammonium hydroxide.
- the solution is then heated to a temperature of between approximately 70 ° C. and approximately 80 ° C., while stirring in order to evaporate the solvents, until a transparent sol-gel precursor is obtained.
- the resulting sol-gel precursor is calcined in an oven at a temperature of about 450 ° C for about 8 hours under an atmosphere of air or oxygen in order to remove the organic content. Finally, the powder thus obtained is ground in a mortar and calcined at a temperature of approximately 900 ° C. for approximately 12 hours.
- Figures 1 to 17 show respectively in (A) the X-ray diffraction diagrams for the lamellar oxide powders of potassium and metal of formulas K 0.67 Ni 0.3 3Mn 0.67 O 2 , K 0, qNi 0.3 Mn 0.7 O 2 , K 0.8 Ni 0.2 5Mn 0.7 5O 2 , K 0.4 Ni 0.2 Mn 0.8 O 2 , K 0.4 Ni 0.2 Mn 0, 6 Ti 0.2 O 2 , K 0.4 Ni 0.2 Mn 0.7 Ti 0, lO 2 , K 0.4 Ni 0.2 Mn 0.7 5Ti 0, 05O 2 , K 0.4 Fe 0.4 Mn 0 6 O 2, K 0.4 Ni 0, LMN 0.9 O 2, K 2 MnO 0.4, K 0.3 Ni 0, 15Mn 0.8 5O 2, K 0.3 Ni 0.2 Mn 0.8 O 2 , K 0.3 MnO 2 , K 0.2 Ni 0.1 Mn 0.9 O 2 , K 0.2 Ni 0.2 Mn 0.8 O 2 ,
- Figure 18 respectively show the X-ray diffraction patterns for potassium lamellar oxide powders and metal Na formulas 0.7 4K 0.08 Ni 0.4 Mn 0.5 9O l 2, Na 0, 6 K 0.08 Ni 0.3 4mn 0, 6 6O 2, Na 0.7 4K 0.08 Ni 0.2 Mn 0.8 O 2, Na 0, 6 K 0.08 Ni 0.2 Mn 0.8 O 2 , Na 0.3 2K 0.08 Ni 0.2 Mn 0.8 O 2 , and Na 0.2 K 0.2 Ni 0.2 Mn 0.8 O 2 .
- Characteristics of the crystal structure The data processing and characterization of the crystal structure was carried out by indexing and comparing the XRD spectra with models from a database to confirm the crystal structure of the lamellar oxides of potassium and of metal.
- Figures 1 to 3 (B) and Figure 9 (C) respectively show an illustration of the crystal structure of lamellar oxides of potassium and metal of formula K 0.67 Ni 0.33 Mn 0.67 O 2 , K 0.6 Ni 0.3 Mn 0.7 O 2 , K 0.5 Ni 0.2 5Mn 0.7 5O 2 , and K 0.4 Ni 0.1 Mn 0.9 O 2 and having the characteristics of crystal structure shown in Table 1.
- Figures 4, 6, 7, 9, 11, 12 and 14 show respectively an illustration of the crystal structure of the lamellar oxides of potassium and metal of the formulas K 0.4 Ni 0.2 Mn 0.8 O 2 , K 0.4 Ni 0.2 Mn 0.7 Ti 0.1 O 2 , K 0.4 Ni 0.2 Mn 0.7 5Ti 0.08 O 2 , K 0.4 Ni 0.1 Mn 0, 9 O 2 , K 0.3 Ni 0.1 sMn 0.85 O 2 , K 0.3 Ni 0.2 Mn 0.8 O 2 and K 0.2 Ni 0.1 Mn 0.9 O 2 , and having the characteristics of crystal structure shown in Table 2.
- FIG. 40 The reflection parameters of lamellar oxides of potassium and metal having the characteristics of the crystal structure shown in Table 2 are shown in Figure 40.
- Figures 8 (B), 14 (C), 15 (B) and 17 (B) respectively show an illustration of the crystal structure of the lamellar oxides of potassium and metal of the formulas K 0.4 Fe 0.4 Mn 0, 6 O 2 , K 0.2 Ni 0.1 Mn 0.9 O 2 , K 0.2 Ni 0.2 Mn 0.8 O 2 , and K 0.1 Ni 0.08 Mn 0.9 5O 2 and having the characteristics of crystal structure shown in Table 3.
- Table 3 Table 3.
- FIG 41 The reflection parameters of the lamellar oxides of potassium and of metal having the characteristics of crystal structure shown in Table 3 are shown in Figure 41.
- Figures 10 and 13 respectively show in (B) an illustration of the crystal structure of the lamellar oxides.
- Figure 16 shows in (B) the characteristics of the crystal structure of a lamellar oxide of potassium and of a metal of formula K 0.2 MnO 2 .
- the main phase consists of a tetragonal manganese oxide Mn 3 O 4 .
- Example 1 The electrochemical properties of the electrochemically active materials as prepared in Example 1 (a) were studied.
- the electrochemical cells were assembled according to the configurations of electrochemical cells presented in Table 5. a) Configurations of the electrochemical cells
- electrochemical cells were assembled in 2032 type button cell cases with the components shown above and negative electrodes including lithium or sodium metallic films on aluminum current collectors.
- the electrochemical cells comprised an electrode material comprising about 80% by weight of electrochemically active material, about 10% by weight of binder (PVDF) and about 10% by weight of electronically conductive material (Ketjen TM black, Super P TM or VGCF ). All electrochemical cells comprising liquid electrolytes were assembled with Celgard TM separators.
- the electrochemical cell separators comprising negative electrodes including a metallic lithium film were impregnated with a 1 M solution of LiPF 6 in an EC / DMC mixture ([4: 6] by volume) in the form of liquid electrolyte and approximately 2% by volume of VC.
- the separators of the electrochemical cells comprising negative electrodes including a metallic sodium film were impregnated with a 1 M solution of NaPF 6 in an EC / DEC ([3: 7] by volume) or EC / DMC ([4: 6] by volume) as a liquid electrolyte.
- b) Electrochemical Behavior of Lamellar Oxides of Potassium and of Metal This example illustrates the electrochemical behavior of electrochemical cells as described in Example 3 (a).
- Figure 19 shows a graph of the capacity (mAh.g 1 ) versus x in a lamellar oxide of potassium and a metal of the formula K x Ni 0.5 xMn 1-0.5 xO 2 recorded for x between 0, 1 and 0.7. The results are presented for a lithium-ion battery (red line) and for a sodium-ion battery (black line). As shown in Figure 19, x can preferably be about 0.4.
- Figures 20 to 37 show the charge and discharge profiles for Cells 1 to 28 and 33 to 35.
- the charge and discharge were performed at 0.1 C between 1.5 V and 4.5 V vs Li + / Li for all electrochemical cells including metallic lithium film as negative electrode and at 0.1 C between 1.5 V and 4.2 V vs Na + / Na for all electrochemical cells including metallic sodium film as a negative electrode.
- Charging and discharging were carried out at a temperature of 25 ° C starting with discharging. The results are presented for a first (black line, 1), a second (red line, 2), and possibly a third (blue line, 3) cycle of discharge and charge.
- the capacities delivered by each of the electrochemical cells are presented in Table 6. Table 6. Capacity delivered by the cells of Table 5
- Figure 38 shows a graph representing the capacity (mAh g -1 ) and the efficiency (%) versus the number of cycles in (A) for Cells 1, 3, 5, 17, 19, 25 and 31; and in (B) for cells 2, 4, 6, 18, 26 and 32.
- the long cycling experiments were carried out at a constant charge and discharge current of C / 10 and at a temperature of about 25 ° vs.
- the results shown in Figure 38 (A) were recorded vs Li + / Li for approximately 45 cycles; and in (B) vs Na + / Na for about 35 cycles.
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Ipc: C01G 49/00 20060101ALI20230711BHEP Ipc: C01G 45/12 20060101ALI20230711BHEP Ipc: C01G 53/00 20060101ALI20230711BHEP Ipc: H01M 4/525 20100101ALI20230711BHEP Ipc: H01M 4/505 20100101ALI20230711BHEP Ipc: H01M 4/485 20100101ALI20230711BHEP Ipc: H01M 10/056 20100101ALI20230711BHEP Ipc: H01M 10/054 20100101ALI20230711BHEP Ipc: H01M 10/0525 20100101ALI20230711BHEP Ipc: H01M 4/131 20100101AFI20230711BHEP |