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EP-4524108-B1 - OXIDATIVE DELITHIATION OF ALKALI NICKEL OXIDE

EP4524108B1EP 4524108 B1EP4524108 B1EP 4524108B1EP-4524108-B1

Inventors

  • ZHANG, FAN
  • CHRISTIAN, PAUL, A.
  • NELSON, JENNIFER, A.
  • ANGLIN, DAVID, L.
  • WILDGUST, PAUL
  • BACCARO, Thomas
  • HU, CHAOLAN

Dates

Publication Date
20260513
Application Date
20211230

Claims (15)

  1. A method of preparing an electrochemically active cathode material, comprising: (a) combining an alkali metal-containing layered nickel oxide having a formula A 1-a Ni 1+a O 2 , wherein A comprises an alkali metal and 0 < a ≤ 0.2, with a fluid composition including a chemical oxidant comprising a peroxydisulfate salt, a monopersulfate salt, or a combination thereof to form a mixture; (b) heating the mixture for at least a period of time sufficient to form a Ni(IV)-containing mixture, the Ni(IV)-containing mixture comprising a Ni(IV)-containing alkali metal-deficient layered nickel oxide electrochemically active cathode material, the Ni(IV) containing mixture having a total nickel (Ni) content; (c) adding to the Ni(IV)-containing mixture of step (b) a mineral acid, wherein the mineral acid is added in an amount of about 0.60 moles or less per mole of total nickel; and (d) heating the mixture of step (c) for at least a period of time sufficient to form an additional amount of the Ni(IV)-containing alkali metal-deficient layered nickel oxide electrochemically active cathode material, the Ni(IV)-containing alkali metal-deficient layered nickel oxide electrochemically active cathode material formed during steps (b) and (d) having the general formula A x H y Ni 1+a O 2 : wherein A comprises an alkali metal; 0.08 ≤ x < 0.2 ; 0 ≤ y < 0.3 ; and 0.02 < a ≤ 0.2 .
  2. The method of claim 1, wherein the alkali metal-containing layered nickel oxide is doped with a metal, M, such that the alkali metal-containing layered nickel oxide has a formula A 1-a Ni 1+a-z M z O 2 , wherein A comprises an alkali metal, 0 < a ≤ 0.2, and 0 ≤ z ≤ 0.2.
  3. The method of claim 1 or claim 2, wherein the (i) oxidant comprises peroxydisulfate salt and/or (ii) wherein A comprises Li.
  4. The method of any one of claims 2 to 3, wherein M comprises a transition metal, a main group metal, or both.
  5. The method of any one of claims 2 to 4, wherein M comprises (a) cobalt (Co), manganese (Mn), iron (Fe), chromium (Cr), vanadium (V), titanium (Ti), niobium (Nb), zirconium (Zr), or a combination thereof; or (b) aluminum (Al), gallium (Ga), bismuth (Bi), or a combination thereof.
  6. The method of any one of the preceding claims, wherein (i) in step (b) the time sufficient to form the Ni(IV) containing mixture is 15 minutes to 6 hours, 15 minutes to 5 hours, 15 minutes to 4 hours, 20 minutes to 4 hours, 20 minutes to 3 hours, 30 minutes to 2 hours, 30 minutes to 1 hour, 15 minutes to 45 minutes, 1 hour to 5 hours, or 2 hours to 4 hours; (ii) in step (d) the time sufficient to form the Ni(IV) containing alkali metal-deficient layered nickel oxide electrochemically active cathode material is 1 hour to 6 hours, 1 hour to 5.5 hours, 1 hour to 5 hours, 2 hours to 4 hours, or 3 hours; and/or (iii) in step (c) the mineral acid comprises sulfuric acid, nitric acid, hydrochloric acid, hydrobromic acid, perchloric acid, hydroiodic acid, or a combination thereof.
  7. The method of any one of the preceding claims, wherein (i) in step (a) the oxidant is provided in an amount between 0.25 and 0.70 moles per mole of the alkali metal-containing layered nickel oxide, preferably in an amount of 0.25 moles, 0.30 moles, 0.35 moles, 0.40 moles, 0.45 moles, 0.50 moles, 0.55 moles, 0.60 moles, 0.65 moles, or 0.70 moles per mole of the alkali metal-containing layered nickel oxide; and/or (ii) in step (b) the temperature is less than 60°C, for example, in a range of 45°C to 55°C, 45°C to 50°C, 50°C to less than 60°C, or 50°C to 55°C.
  8. The method of any one of the preceding claims, wherein (i) in step (c) the mineral acid is provided in an amount of 0.40 to 0.55 moles per mole of the total nickel, 0.45 to 0.55, 0.50 to 0.55, 0.40 to 0.45, 0.45 to 0.50 moles of mineral acid per mole of the total nickel; and/or (ii) in step (d) the temperature is 60°C to 80°C, 60°C to 75°C, 60°C to 70°C, 65°C to 75°C, 68°C to 72°C, 60°C, 65°C, 70°C, 75°C, or 80°C.
  9. The method of any one of claims 1 to 6, wherein (i) in step (a) the oxidant is provided in an amount of 1 mole per mole of the alkali metal-containing layered nickel oxide, or in a range of 1 to 2 moles of oxidant, 1.3 to 2 moles of oxidant, 1.5 to 2 moles of oxidant, 1 to 1.9 moles of oxidant, 1.3 to 1.8 moles or oxidant, or 1.4 to 1.7 moles of oxidant per mole of the alkali metal-containing layered nickel oxide; and/or (ii) in step (b) the temperature is a temperature of 45°C to less than 60°C, 45°C to 55°C, 45°C to 50°C, 50°C to less than 60°C, or 50°C to 55°C.
  10. The method of claim 9, wherein in step (c) the mineral acid is provided in an amount of 0.20 moles to 0.40 moles per mole of the total nickel, or 0.25 moles to 0.35 moles per mole of the total nickel, or 0.30 moles per mole of the total nickel; and/or wherein in step (d) the temperature is 60°C to 80°C, 60°C to 75°C, 60°C to 70°C, 65°C to 75°C, 68°C to 72°C, 60°C, 65°C, 70°C, 75°C, or 80°C.
  11. The method of any one of the preceding claims, wherein (i) the oxidant comprises a counter cation selected from the group consisting of ammonium, sodium, potassium, lithium, or a combination thereof; (ii) x has a value of 0.01 to 0.20, 0.01 to 0.18, 0.01 to 0.16, 0.01 to 0.15, 0.02 to 0.20, 0.02 to 0.18, 0.02 to 0.16, 0.02 to 0.15, 0.03 to 0.20, 0.03 to 0.19, 0.03 to 0.15, 0.03 to 0.12, 0.05 to 0.19, or 0.05 to 0.15; (iii) wherein z has a value of 0 to 0.20, 0.01 to 0.20, 0.01 to 0.18, 0.01 to 0.16, 0.01 to 0.15, 0.02 to 0.20, 0.02 to 0.18, 0.02 to 0.16, 0.02 to 0.15, 0.03 to 0.20, 0.03 to 0.19, 0.03 to 0.15, 0.03 to 0.12, 0.05 to 0.19, or 0.05 to 0.15; (iv) wherein y has a value of 0 to 0.29, 0.05 to 0.25, 0.5 to 0.20, 0.5 to 0.15, 0.08 to 0.29, 0.08 to 0.25, 0.08 to 0.20, 0.08 to 0.15, 0.10 to 0.29, 0.10 to 0.25, 0.10 to 0.20, or 0.10 to 0.15; and/or (v) a has a value of 0.02 to 0.20, 0.02 to 0.18, 0.02 to 0.16, 0.02 to 0.15, 0.03 to 0.20, 0.03 to 0.18, 0.03 to 0.16, 0.03 to 0.15, 0.04 to 0.20, 0.04 to 0.18, 0.04 to 0.15, 0.04 to 0.12, 0.05 to 0.19, or 0.05 to 0.15.
  12. The method of any one of the preceding claims, wherein (i) in step (a) the alkali metal-containing layered nickel oxide and the oxidant are provided in a molar ratio of 1 mol alkali metal-containing layered nickel oxide :0.25 mol oxidant to 1 mol alkali metal-containing layered nickel oxide :0.70 mol oxidant, which equals to 1:0.25 to 1:0.70, 1:0.25 to 1:0.65, 1:0.25 to 1:0.60, 1:0.25 to 1:0.50, 1:0.25 to 1:0.45, 1:0.30 to 1:0.70, 1:0.30 to 1:0.65, 1:0.30 to 1:0.55, 1:0.30 to 1:0.45, 1:0.35 to 1:0.70, 1:0.35 to 1:0.65, 1:0.35 to 1:0.60, 1:0.35 to 1:0.55, 1:0.35 to 1:0.50, 1:0.35 to 1:0.45, or 1:0.35 to 1:0.40; and/or (ii) in step (a) the fluid composition has a pH in a range of 4 to 12, 4 to 11, 4 to 10, or 4 to 9, 9 to 12, 10 to 12, or 11 to 12.
  13. The method of any one of the preceding claims, further comprising treating the Ni(IV)-containing alkali metal-deficient nickel oxide with an aqueous solution of an alkali hydroxide to form a compound according to the formula: A x A' v Ni 1+a O 2 ·nH 2 O or A x A' v Ni 1+a-z M z O 2 ·nH 2 O, wherein A comprises Li, or Na; M comprises a transition metal; A' comprises K, Rb or Cs; 0.04 ≤ x < 0.2 ; 0.03 < v < 0.20 ; 0.02 ≤ a ≤ 0.2 ; 0 ≤ z ≤ 0.2 ; and 0 < n < 2 .
  14. The method of claim 13, wherein (a) the alkali hydroxide comprises potassium hydroxide, rubidium hydroxide, cesium hydroxide, or a combination thereof; and/or (b) A comprises Li and A' comprises K.
  15. The method of any one of claims 1 to 8 or 11 to 12, wherein in step (a) the oxidant comprises a peroxydisulfate salt and is provided in an amount of 0.25 to 0.45 moles per mole of the alkali metal-containing layered nickel oxide, in step (b) the mixture is heated to a temperature of 45°C to 55°C for 2 to 4 hours, in step (c) the mineral acid comprises sulfuric acid and is provided in an amount of 0.4 to 0.55 moles per mole of the total nickel, and in step (d) the mixture is heated to a temperature of 65°C to 75°C for 2 to 4 hours.

Description

FIELD OF THE DISCLOSURE The disclosure relates generally to the oxidative demetallation of an alkali nickel oxide. More specifically, the disclosure relates to the oxidative demetallation of an alkali nickel oxide using a multi-step hybrid process including treatment with a persulfate salt and separate, subsequent treatment with a mineral acid. BACKGROUND Alkali metal-containing transition metal oxides can be energetically activated or "charged" for the purpose of preparing highly oxidized cathode materials for use in both primary and secondary electrochemical cells. Charging of the alkali metal-containing transition metal oxides comprises oxidation of the transition metal and removal of the alkali metal from the metal oxide crystal lattice, in part or in whole, to form an alkali metal-deficient transition metal oxide electrochemically active cathode material. The alkali metal-containing transition metal oxides can be chemically charged or electrochemically charged. Methods of chemically charging the alkali metal-containing transition metal oxides can include oxidative demetallation and acid-promoted disproportionation of the transition metal, e.g., by treatment with a mineral acid. It is known that acid-promoted disproportionation of alkali metal-containing transition metal oxides including metals such as Mn and Ni results in extraction of essentially all the alkali metal ions present from the crystal lattice as well as oxidation of at most 50% of the metal, for example from an M(III) oxidation state to an M(IV) oxidation state. A corresponding amount of the M(III) is reduced to M(II), which dissolves in the acid solution. The acid-promoted disproportionation reaction can be summarized, using stoichiometric layered lithium nickel oxide as an example, as follows in Equation 1: LiNiO2+2yH2SO4→1−yLi1-2y/1−yNiO2+yNiSO4+yLi2SO4+2yH2O0≤y≤12. The Ni(ll) ions are soluble and dissolve in the aqueous acid solution. Thus, use of an acid-promoted metal disproportionation reaction to chemically charge an alkali metal containing transition metal oxide is very inefficient since at least half of the M(III) ions in the starting transition metal oxide are reduced to M(II) ions that can dissolve in the acid solution and, thus, are extracted out of the crystal structure Further, the dissolution of M(II) ions results in a reduction in the average particle size of the transition metal oxide. Chemically charging an alkali metal-containing transition metal oxide with a strong, soluble chemical oxidant can be used to directly oxidize the transition metal to a higher oxidation state and result in the removal of a proportional amount of alkali metal ions to maintain overall electroneutrality of the crystal lattice. Various reagents such as strongly oxidizing gases (e.g., ozone, chlorine or bromine), strongly oxidizing solid reagents (e.g., nitrosonium hexafluorophosphate, nitrosonium tetrafluorborate, nitrosonium hexafluoroarsenate, nitronium tetrafluoroborate, nitronium hexafluorophosphate, nitronium hexafluoroarsenate), and water soluble oxidizing agents (e.g., alkali or alkaline earth metal hypochlorites (e.g., Na+, K+, Ca2+), alkali peroxydisulfates (e.g., Na+, K+), ammonium peroxydisulfate, and alkali monopersulfates (e.g., Na+, K+) have been used to chemically charge alkali metal-containing transition metal oxides. Other water soluble oxidizing agents include alkali permanganates (e.g., K+, Na+, Li+) and alkali ferrates (e.g., K+). Methods using water soluble oxidizing agents are typically performed near room temperature over 24 to 48 hours; however such methods often lack sufficient oxidation strengths to rapidly and sufficiently oxidize the transition metal and demetallate the starting alkali metal-containing transition metal oxide to prepare an alkali metal-deficient metal oxide having a formula of AxMO2 or AxM2O4 where A is the alkali metal and M is the transition metal, for example, wherein x is less than about 0.3. US 2018/331361 discloses non-stoichiometric beta-delithiated layered nickel oxide having a chemical formula. The chemical formula is LixAyNi1+a-zMzO2 with 0.02 ≤ x ≤ 0.20; 0.03 ≤ y ≤ 0.2; 0.02 ≤ a ≤ 0.2; 0 ≤ z ≤ 0.2; and 0 ≤ n ≤ 1. Within the chemical formula, A is an alkali metal and includes potassium, rubidium, cesium, and any combination thereof. Within the chemical formula M comprises an alkaline earth metal, a transition metal, a non-transition metal, and any combination thereof. The method for producing the non-stoichiometric betadelithiated layered nickel oxide is described in only a general manner, starting from nonstoichiometric lithium nickelate, which is chemically oxidized to form first a non-stoichiometric alpha-delithiated layered nickel oxide. As suitable oxidants, sodium hypochlorite, sodium peroxydisulfate, potassium peroxydisulfate, ammonium peroxydisulfate, sodium permanganate, potassium permanganate, sodium dichromate, potassium dichromate, ozone gas, chlorine gas, bromine gas, sulfuric ac