Immobilized selenium, a method of making, and uses of immobilized selenium in a rechargeable battery

Patent metadata

Field	Value
Publication number	US-11515518-B2
Application number	US-202016898900-A
Country	US
Kind code	B2
Filing date	Jun 11, 2020
Priority date	Sep 22, 2015
Publication date	Nov 29, 2022
Grant date	Nov 29, 2022

Abstract

An immobilized selenium body, made from carbon and selenium and optionally sulfur, makes selenium more stable, requiring a higher temperature or an increase in kinetic energy for selenium to escape from the immobilized selenium body and enter a gas system, as compared to selenium alone. Immobilized selenium localized in a carbon skeleton can be utilized in a rechargeable battery. Immobilization of the selenium can impart compression stress on both the carbon skeleton and the selenium. Such compression stress enhances the electrical conductivity in the carbon skeleton and among the selenium particles and creates an interface for electrons to be delivered and or harvested in use of the battery. A rechargeable battery made from immobilized selenium can be charged or discharged at a faster rate over conventional batteries and can demonstrate excellent cycling stability.

First claim

The invention claimed is:

1. A rechargeable battery comprising:
a cathode comprised of immobilized selenium disposed on an electrically conductive substrate;
a separator disposed in direct contact with the immobilized selenium; and
an anode spaced from the cathode by the separator, wherein an activation energy for a selenium particle to escape the immobilized selenium is ≥95 kJ/mole, wherein the immobilized selenium has a mid-point weight-loss temperature ≥520 C.

2. The rechargeable battery of claim 1 , further including the anode spaced from the separator by lithium.

3. The rechargeable battery of claim 2 , further including the cathode, the separator, the anode, and the lithium immersed in an electrolyte.

4. The rechargeable battery of claim 1 , wherein the immobilized selenium comprises a selenium-carbon mixture, wherein the selenium has been melted into the carbon.

5. The rechargeable battery of claim 1 , wherein the separator is formed from an organic material, an inorganic material, or a solid electrolyte.

6. The rechargeable battery of claim 1 , comprising at least one of the following:
an electrochemical capacity of ≥400 mAh/g of selenium;
chargeable at ≥0.1C;
a specific capacity of >30% of a second discharge capacity at a charge-discharge cycling rate of 0.1C following charge-discharge cycling at 5 cycles at 0.1C, 5 cycles at 0.2C, 5 cycles at 0.5C, 5 cycles at 1C, 5 cycles at 2C, 5 cycles at 5C, and 5 cycles at 10C; and
a Coulombic efficiency ≥50%.

7. A rechargeable battery comprising:
a cathode comprised of immobilized sulfur-doped selenium disposed on an electrically conductive substrate;
a separator disposed in direct contact with the immobilized sulfur-doped selenium; and
an anode spaced from the cathode by the separator, wherein an activation energy for a selenium particle to escape the immobilized sulfur-doped selenium is ≥95 kJ/mole, wherein the immobilized sulfur-doped selenium has a mid-point weight-loss temperature ≥520 C.

8. The rechargeable battery of claim 7 , further including the anode spaced from the separator by lithium.

9. The rechargeable battery of claim 7 , further including the cathode, the separator, the anode, and the lithium immersed in an electrolyte.

10. The rechargeable battery of claim 7 , wherein the immobilized sulfur-doped selenium comprises a selenium-carbon-sulfur mixture, wherein the selenium and sulfur has been melted into the carbon.

11. The rechargeable battery of claim 7 , wherein the separator is formed from an organic material, an inorganic material, or a solid electrolyte.

12. The rechargeable battery of claim 7 , comprising a Coulombic efficiency ≥95%.

13. An immobilized selenium body comprised of a mixture of selenium and carbon, said immobilized selenium body comprising:
an activation energy for a selenium particle to escape the immobilized selenium body is ≥95 kJ/mole; and
a mid-point weight-loss temperature ≥520° C.

14. The immobilized selenium body of claim 13 , wherein said immobilized selenium body further comprises a kinetic energy for a selenium particle to escape the immobilized selenium body ≥9.5 kJ/mole.

15. The immobilized selenium body of claim 13 , wherein said immobilized selenium body further comprises a temperature for a selenium particle to escape the immobilized selenium body ≥490° C.

16. The immobilized selenium body of claim 13 , wherein said immobilized selenium body further comprises the carbon including pores less than 20 angstroms, wherein for said pores less than 20 angstroms, the carbon has a surface area ≥400 m 2 /g.

17. The immobilized selenium body of claim 13 , wherein said immobilized selenium body further comprises the carbon including pores between 20 angstroms and 1000 angstroms, wherein for said pores between 20 angstroms and 1000 angstroms, the carbon has a surface area ≤20% of the total surface area.

18. The immobilized selenium body of claim 13 , wherein said immobilized selenium body further comprises the carbon, the selenium, or both are under compression.

19. The immobilized selenium body of claim 13 , wherein said immobilized selenium body further comprises a collision frequency for the selenium in the immobilized selenium body ≥2.5×10 5 .

20. The immobilized selenium body of claim 13 , wherein said immobilized selenium body further comprises, at 50° C., the immobilized selenium body has a kinetic rate constant ≤1×10 −10 .

21. The immobilized selenium body of claim 13 , wherein the selenium is an elemental form of selenium, a compound form of selenium, or both.

22. The immobilized selenium body of claim 13 , wherein the immobilized selenium body comprises, in addition to selenium and carbon, at least one other element from Group 6 of the Periodic Table in a concentration between 100 ppm by weight of the immobilized selenium body and 85% of the total weight of the immobilized selenium body.

23. The immobilized selenium body of claim 13 , wherein:
the selenium includes interfacial selenium; and
a kinetic energy for a selenium particle to escape the interfacial selenium of the immobilized selenium body ≥11,635 joules/mole at a temperature ≥660° C.

24. The immobilized selenium body of claim 13 , wherein said immobilized selenium body includes ≥5% selenium.

25. The immobilized selenium body of claim 13 , wherein said immobilized selenium body has a Raman peak intensity at 255±25 cm −1 .

26. The immobilized selenium body of claim 13 , wherein:
the carbon of said immobilized selenium body defines a carbon skeleton;
the carbon skeleton has Sp 2 -carbon-carbon bonds with D-band and G-band Raman peaks; and
a ratio of areas of the D-band to the G-band is between 0.01 and 100.

27. The immobilized selenium body of claim 26 , wherein the carbon skeleton has a Raman D-band located at 1365±100 cm −1 and a Raman G-band located at 1589±100 cm −1 .

Assignees

• Ii Vi Delaware Inc
• Inst Chemistry Cas

Inventors

• Eissler Elgin E
• Xu Wen-Qing
• Zhang Yancheng
• Li Xiaoming
• Patkar Shailesh
• Barbarossa Giovanni
• Guo Yu-Guo
• Zhang Shuaifeng
• Yin Yaxia

Classifications

• H01M50/414

  Synthetic resins, e.g. thermoplastics or thermosetting resins · CPC title

• H01M50/417

  Polyolefins · CPC title

• H01M4/58

  of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates · CPC title

• H01M10/0525

  Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries · CPC title

• H01M4/625

  Carbon or graphite · CPC title