Sodium ion-based internal hybrid electrochemical energy storage cell

Patent metadata

Field	Value
Publication number	US-10566668-B2
Application number	US-201715727900-A
Country	US
Kind code	B2
Filing date	Oct 9, 2017
Priority date	Oct 9, 2017
Publication date	Feb 18, 2020
Grant date	Feb 18, 2020

Abstract

Provided is an internal hybrid electrochemical cell comprising: (a) a pseudocapacitance-like cathode comprising a cathode active material that contains both graphene sheets and a porphyrin compound, including porphyrin or a porphyrin complex, wherein the porphyrin compound is bonded to or supported by primary surfaces of graphene sheets to form a redox pair for pseudocapacitance; (b) a battery-like anode comprising an anode active material selected from sodium metal, a sodium metal alloy, a sodium intercalation compound, a sodium-containing compound, or a combination thereof, and (c) a sodium-containing electrolyte in physical contact with the anode and the cathode; wherein the cathode active material has a specific surface area no less than 100 m2/g which is in direct physical contact with the electrolyte.

First claim

We claim:

1. An internal hybrid electrochemical cell comprising:
(A) a cathode comprising a cathode active material that contains both graphene sheets and a porphyrin compound, wherein said porphyrin compound is bonded to or supported by primary surfaces of said graphene sheets to form a redox pair for pseudocapacitance;
(B) an anode comprising an anode active material selected from sodium metal, a sodium metal alloy, a sodium intercalation compound, a sodium-containing compound, or a combination thereof; and
(C) a sodium-containing electrolyte in physical contact with the anode and the cathode; wherein said cathode active material has a specific surface area no less than 100 m 2 /g which is in direct physical contact with said electrolyte.

2. An internal hybrid electrochemical cell comprising:
a) a cathode comprising a cathode active material that contains a porphyrin compound and a carbon material, wherein said porphyrin compound is bonded to or supported by a surface of said carbon material to form a redox pair for pseudocapacitance and said carbon material is selected from activated carbon, activated carbon black, expanded graphite flakes, exfoliated graphite worms, carbon nanotube, carbon nanofiber, carbon fiber, a combination thereof, or a combination thereof with graphene;
b) an anode comprising an anode active material selected from sodium metal, a sodium metal alloy, a sodium intercalation compound, a sodium-containing compound, or a combination thereof; and
c) a sodium-containing electrolyte in physical contact with the anode and the cathode; wherein said cathode active material has a specific surface area no less than 100 m 2 /g which is in direct physical contact with said electrolyte.

3. The internal hybrid electrochemical cell of claim 1 , wherein said activated carbon is selected from chemically etched or expanded soft carbon, chemically etched or expanded hard carbon, exfoliated activated carbon, chemically etched multi-walled carbon nanotube, nitrogen-doped carbon nanotube, boron-doped carbon nanotube, chemically doped carbon nanotube, ion-implanted carbon nanotube, chemically treated multi-walled carbon nanotube with an inter-planar separation no less than 0.4 nm, chemically expanded carbon nanofiber, activated carbon fiber, activated graphite fiber, activated carbonized polymer fiber, activated coke, activated pitch, activated asphalt, activated mesophase carbon, activated mesoporous carbon, activated electrospun conductive nanofiber, or a combination thereof.

4. The internal hybrid electrochemical cell of claim 1 or claim 2 , wherein said sodium intercalation compound is selected from pre-sodiated coke, pre-sodiated carbon black, pre-sodiated amorphous carbon, pre-sodiated activated carbon, pre-sodiated hard carbon, pre-sodiated soft carbon, pre-sodiated hollow carbon nanowires, pre-sodiated hollow carbon sphere, pre-sodiated carbon nanotubes, pre-sodiated carbon fibers, pre-sodiated expanded graphite, pre-sodiated graphene, sodium titanates, pre-sodiated V 2 O 5 , pre-sodiated Nb 2 O 5 , pre-sodiated NiCo 2 O 4 , Na 3 V 2 (PO 4 ) 3 , NaTi 2 (PO 4 ) 3 , Na 2 Ti 3 O 7 , Na 2 C 8 H 4 O 4 , Na 2 TP, Na x TiO 2 (x=0.2 to 1.0), Na 2 Fe 2 (SO 4 ) 3 , Na 2 C 8 H 4 O 4 , carboxylate based materials, C 8 H 4 Na 2 O 4 , pre-sodiated C 8 H 6 O 4 , C 8 H 5 NaO 4 , C 8 Na 2 F 4 O 4 , C 10 H 2 Na 4 O 8 , pre-sodiated C 14 H 4 O 6 , C 14 H 4 Na 4 O 8 , a pre-sodiated member of MXenes, or a combination thereof.

5. The internal hybrid electrochemical cell of claim 1 or claim 2 , wherein said sodium intercalation compound or sodium-containing compound is selected from the group consisting of:
A) sodium-doped silicon (Si), germanium (Ge), tin (Sn), lead (Pb), antimony (Sb), bismuth (Bi), zinc (Zn), aluminum (Al), titanium (Ti), cobalt (Co), nickel (Ni), manganese (Mn), cadmium (Cd), and mixtures thereof;
B) sodium-containing alloys or intermetallic compounds of Si, Ge, Sn, Pb, Sb, Bi, Zn, Al, Ti, Co, Ni, Mn, Cd, and their mixtures;
C) sodium-containing oxides, carbides, nitrides, sulfides, phosphides, selenides, tellurides, or antimonides of Si, Ge, Sn, Pb, Sb, Bi, Zn, Al, V, Fe, Ti, Co, Ni, Mn, Cd, and mixtures or composites thereof; and
D) combinations thereof and combinations thereof with a pre-sodiated carbon or graphite material.

6. The internal hybrid electrochemical cell of claim 1 or claim 2 , wherein said porphyrin compound is selected from porphyrin, porphyrin-copper, porphyrin-zinc, porphyrin-nickel, porphyrin-cobalt, porphyrin-manganese, porphyrin-iron, porphyrin-tin, porphyrin-cadmium, porphyrin-vanadium, polyporphyrin, a functionalized porphyrin compound, or a combination thereof.

7. The internal hybrid electrochemical cell of claim 1 or claim 2 , wherein said porphyrin compound is selected from a porphyrin-transition metal complex.

8. The internal hybrid electrochemical cell of claim 1 or claim 2 , wherein said porphyrin compound contains a functionalized porphyrin compound having at least a functional group attached to a porphyrin molecule, wherein said functional group is selected from OY, NHY, O═C—OY, P═C—NR′Y, O═C—SY, O═C—Y, —CR′1-OY, N′Y or C′Y, and Y is a functional group of a protein, a peptide, an amino acid, an enzyme, an antibody, a nucleotide, an oligonucleotide, an antigen, or an enzyme substrate, enzyme inhibitor or the transition state analog of an enzyme substrate or is selected from a phenol group, R′—OH, R′—NR′ 2 , R′SH, R′CHO, R′CN, R′X, R′N + (R′) 3 X − , R′SiR′ 3 , R′Si(—OR′—) y R′ 3-y , R′Si(—O—SiR′ 2 —) OR′, R′—R″, R′—N—CO, (C 2 H 4 O—) w H, (—C 3 H 6 O—) w H, (—C 2 H 4 O) w —R′, (C 3 H 6 O) w —R′, R′, and w is an integer greater than one and less than 200.

9. The internal hybrid electrochemical cell of claim 1 or claim 2 , wherein said porphyrin compound contains a functionalized porphyrin compound having at least a functional group attached to a porphyrin molecule, wherein said functional group is selected from the group consisting of amidoamines, polyamides, aliphatic amines, modified aliphatic amines, cycloaliphatic amines, aromatic amines, anhydrides, ketimines, diethylenetriamine (DETA), triethylene-tetramine (TETA), tetraethylene-pentamine (TEPA), polyethylene polyamine, polyamine epoxy adduct, phenolic hardener, non-brominated curing agent, non-amine curatives, and combinations thereof.

10. The internal hybrid electrochemical cell of claim 1 or claim 2 , wherein said porphyrin compound contains a functionalized porphyrin compound having at least a functional group attached to a porphyrin molecule, wherein said functional group contains an azide or bi-radical compound selected from the group consisting of 2-Azidoethanol, 3-Azidopropan-1-amine, 4-(2-Azidoethoxy)-4-oxobutanoic acid, 2-Azidoethyl-2-bromo-2-methylpropanoate, chlorocarbonate, azidocarbonate, dichlorocarbene, carbene, aryne, nitrene, (R-)-oxycarbonyl nitrenes, where R=any one of the following groups,

and combinations thereof.

11. The internal hybrid electrochemical cell of claim 1 , wherein said graphene sheets comprise single-layer or few-layer graphene, containing up to 10 graphene planes, selected from pristine graphene, graphene oxide, reduced graphene oxide, halogenated graphene, hydrogenated graphene, nitrogenated graphene, doped graphene, chemically functionalized graphene, or a combination thereof.

12. The internal hybrid electrochemical cell of claim 1 or claim 2 , wherein said cathode active material has a specific surface area no less than 200 m 2 /g which is in direct physical contact with said electrolyte and said graphene sheets contain sing

Assignees

• Nanotek Instruments Inc
• Nanotek Instr Group Llc

Inventors

• Chai Songhai
• Lin Yen-Po
• Zhamu Aruna
• Jang Bor Z

Classifications

• H01G11/32

  Carbon-based · CPC title

• H01G11/24

  characterised by structural features of the materials making up or comprised in the electrodes, e.g. form, surface area or porosity; characterised by the structural features of powders or particles used therefor · CPC title

• H01M4/583

  Carbonaceous material, e.g. graphite-intercalation compounds or CFx · CPC title

• H01M2300/0002

  Aqueous electrolytes · CPC title

• H01G11/30

  characterised by their material · CPC title