One-dimensional structure pre-calciated materials as positive electrode for rechargeable calcium batteries and cell comprising the same

Patent metadata

Field	Value
Publication number	US-11489157-B2
Application number	US-201816760258-A
Country	US
Kind code	B2
Filing date	Jan 8, 2018
Priority date	Nov 16, 2017
Publication date	Nov 1, 2022
Grant date	Nov 1, 2022

Abstract

The present invention relates to a calcium-based secondary cell containing:an electrolyte arranged between the negative electrode and the positive electrode and comprising a calcium salt of a fluorine-containing anion of formula (XFn)m− wherein n is a positive integer of at most 6 and m is a positive integer of at least 1 and m<n,a positive-electrode active material at the positive electrode which is a one-dimensional structure accommodating Ca2+ ions and has the formula (1):Can+2Me1(n+1)−y−zMe2yMe3zO3n+3  (1)wherein:Me1, Me2, Me3 are different transition metals;1≤n and n is not necessarily an integer;0≤y and y is not necessarily an integer;0≤z and z is not necessarily an integer.

First claim

The invention claimed is:

1. A calcium-based secondary cell comprising:
a negative electrode that includes a negative-electrode active material, said negative-electrode active material being capable of accepting and releasing calcium ions,
a positive electrode that includes a positive-electrode active material, said positive-electrode active material being capable of accepting and releasing calcium ions,
an electrolyte arranged between the negative electrode and the positive electrode and comprising a calcium salt of a fluorine-containing anion of formula (XF n ) m− wherein n is a positive integer of at most 6 and m is a positive integer of at least 1 and m<n,
wherein the positive-electrode active material is a one-dimensional structure accommodating Ca 2+ ions and has the formula (1):
Ca n+2 Me1 (n+1)−y−z Me2 y Me3 z O 3n+3   (1)

wherein, in formula (1):
Me1, Me2, Me3 are different transition metals;
1≤n and n is not necessarily an integer;
0≤y and y is not necessarily an integer;
0≤z and z is not necessarily an integer,
wherein the negative electrode comprises from 50 weight % to 100 weight % of metallic calcium or a calcium alloy according to the formula (I) when a total weight of the negative electrode is 100 weight %:
Ca m B  (I)

wherein, in Formula (I), m is 0≤m≤3, and B is a metal or a semi-conductor element.

2. The calcium-based secondary cell according to claim 1 , wherein the central atom X, in the anion part of the calcium salt of a fluorine-containing anion, is a three- to six-valent atom from one of groups 13 to 16 of the Periodic Table.

3. The calcium-based secondary cell according to claim 1 , wherein the calcium salt of a fluorine-containing anion is Ca(BF 4 ) 2 and/or Ca(PF 6 ) 2 .

4. The calcium-based secondary cell according to claim 1 , wherein Me1, Me2 and Me3 are each independently chosen among Ni, Mn, Co, Cr and Fe.

5. The calcium-based secondary cell according to claim 1 , wherein y and z are not both zero at the same time.

6. The calcium-based secondary cell according to claim 5 , wherein the positive-electrode active material is a one-dimensional structure having a formula chosen in the group consisting of: Ca 3 NiMnO 6 ; Ca 3 CoMnO 6 ; Ca 3 CoFeO 6 ; Ca 3 Co 0.5 Fe 0.5 MnO 6 ; Ca 3 CrNiO 6 ; Ca 6 Co 3 NiCrO 15 ; and Ca 6 Co 2 N 12 MnO 15 .

7. The calcium-based secondary cell according to claim 1 , wherein y and z are both zero at the same time.

8. The calcium-based secondary cell according to claim 7 , wherein the positive-electrode active material is a one-dimensional structure having a formula chosen in the group consisting of: Ca 3 Co 2 O 6 ; CaCoO 3 .

9. The cell according to claim 1 , wherein the negative electrode material is a calcium metal anode.

10. The cell according to claim 1 , wherein the calcium-based secondary cell includes a positive current collector, and the positive current collector is based on aluminum.

11. The cell according to claim 1 , wherein the electrolyte contains a mixture of ethylene carbonate (EC) and propylene carbonate (PC).

12. The cell according to claim 1 , wherein the cell further comprises a temperature control element.

13. The cell according to claim 1 , wherein the negative electrode comprises from 65 weight % to 100 weight % of the metallic calcium or the calcium alloy.

14. The cell according to claim 1 , wherein the negative electrode comprises from 75 weight % to 100 weight % of the metallic calcium or the calcium alloy.

15. The cell according to claim 1 , wherein the negative electrode active material consists of the metallic calcium or the calcium alloy.

16. The cell according to claim 1 , wherein the negative electrode active material is the calcium alloy, and the calcium alloy comprises Ca x Sn y or Ca x Si y and 0≤x≤2.

17. The cell according to claim 13 , wherein the negative electrode active material is the calcium alloy, and the calcium alloy comprises Ca x Sn y or Ca x Si y and 0≤x≤2.

18. A non-aqueous calcium-based secondary battery comprising a calcium-based secondary cell according to claim 1 .

19. A vehicle, an electronic device, a robot, a wheelchair, an autonomous drone or a stationary power generating device comprising a non-aqueous calcium-based secondary battery according to claim 18 .

Assignees

• Toyota Motor Europe
• Agencia Estatal Consejo Superior De Investig Cientificas

Inventors

• Barde Fanny
• Palacin Maria Rosa
• Stoytcheva Deyana
• Ponrouch Alexandre
• Frontera Carlos

Classifications

• H01M2300/0025

  Organic electrolyte · CPC title

• H01M10/0568 Primary

  characterised by the solutes · CPC title

• H01M4/525 Primary

  of mixed oxides or hydroxides containing iron, cobalt or nickel for inserting or intercalating light metals, e.g. LiNiO2, LiCoO2 or LiCoOxFy · CPC title

• H01M10/054

  Accumulators with insertion or intercalation of metals other than lithium, e.g. with magnesium or aluminium · CPC title

• H01M10/63

  Control systems (charging or discharging in response to temperature H01M10/44 {, H01M10/443}; measurement of temperature H01M10/48 {, H01M10/486}) · CPC title