Sodium ion based aqueous electrolyte electrochemical secondary energy storage device

Abstract

A secondary hybrid aqueous energy storage device includes an anode electrode, a cathode electrode which is capable of reversibly intercalating sodium cations, a separator, and a sodium cation containing aqueous electrolyte, wherein an initial active cathode electrode material comprises an alkali metal containing active cathode electrode material which deintercalates alkali metal ions during initial charging of the device.

1 . A secondary hybrid aqueous energy storage device, comprising: an anode electrode, a cathode electrode which is capable of reversibly intercalating sodium cations, a separator, and a sodium cation containing aqueous electrolyte, wherein an initial active cathode electrode material in the device comprises an alkali metal containing active cathode electrode material which deintercalates alkali metal ions during initial charging of the device. 
   
   
       2 . The device of  claim 1 , wherein the anode electrode comprises a double-layer capacitor electrode which stores charge through a reversible nonfaradiac reaction of alkali metal cations on a surface of the anode electrode or a pseudocapacitive electrode which undergoes a partial charge transfer surface interaction with alkali metal cations on a surface of the anode electrode. 
   
   
       3 . The device of  claim 1 , wherein the initial active cathode electrode material comprises a transition metal oxide, sulfide, phosphate or fluoride. 
   
   
       4 . The device of  claim 3 , wherein the initial active cathode electrode material comprises a transition metal oxide. 
   
   
       5 . The device of  claim 4 , wherein the active cathode electrode material comprises a doped or undoped cubic spinel λ-MnO 2 -type material. 
   
   
       6 . The device of  claim 5 , wherein the doped or undoped cubic spinel λ-MnO 2 -type material is formed by providing a lithium manganate cubic spinel material and then removing at least a portion of the lithium during the initial charging to form the λ-MnO 2 -type material. 
   
   
       7 . The device of  claim 5 , wherein the doped or undoped cubic spinel λ-MnO 2 -type material is formed by providing a lithium manganate cubic spinel material, chemically or electrochemically removing at least a portion of the lithium, and performing a chemical or electrochemical ion exchange to insert sodium into alkali metal sites of the λ-MnO 2 -type material. 
   
   
       8 . The device of  claim 5 , wherein the doped or undoped cubic spinel λ-MnO 2 -type material comprises Al-doped cubic spinel λ-MnO 2 . 
   
   
       9 . The device of  claim 5 , wherein the doped or undoped cubic spinel λ-MnO 2 -type material comprises Al-doped, and at least one of lithium, sodium, potassium, calcium, or magnesium containing cubic spinel λ-MnO 2 . 
   
   
       10 . The device of  claim 3 , wherein the initial active cathode electrode material comprises a doped or undoped layered orthorhombic NaMnO 2  birnessite material. 
   
   
       11 . The device of  claim 3  wherein the initial active cathode electrode material comprises a Na 2 M 3 O 7  material, wherein M comprises at least one transition metal. 
   
   
       12 . The device of  claim 3 , wherein the initial active cathode electrode material comprises a doped or undoped NaMPO 4  material, wherein M comprises at least one transition metal. 
   
   
       13 . The device of  claim 3 , wherein the initial active cathode electrode material comprises a doped or undoped NaM 2 (PO 4 ) 3  material, wherein M comprises at least one transition metal. 
   
   
       14 . The device of  claim 3 , wherein the initial active cathode electrode material comprises a doped or undoped Na 2 MPO 4 F material, wherein M comprises at least one transition metal. 
   
   
       15 . The device of  claim 3 , wherein the initial active cathode electrode material comprises a doped or undoped tunnel-structured Na 0.44 MO 2  material, wherein M comprises at least one transition metal. 
   
   
       16 . The device of  claim 3 , wherein the transition metal is one or more transition metals selected from the group consisting of Mn, Fe, Co, Ni, Cr, V, Ti, Cu, Zr, Nb, W, and Mo. 
   
   
       17 . The device of  claim 3 , wherein the anode comprises porous activated carbon, graphite, mesoporous carbon, carbon nanotubes, disordered carbon, Ti-oxide material, V-oxide material, phospho-olivine material, mesoporous ceramic material, or a composite thereof. 
   
   
       18 . The device of  claim 17 , wherein the electrolyte comprises Na 2 SO 4 , NaNO 3 , NaClO 4 , Na 3 PO 4 , Na 2 CO 3 , NaCl, NaOH, or combination thereof. 
   
   
       19 . The device of  claim 17 , wherein the electrolyte solution further comprises one or more salts comprising potassium, calcium, or magnesium. 
   
   
       20 . The device of  claim 1 , further comprising a cathode current collector which comprises a Ni mesh, a coated Al foil, Ti, or stainless steel, and an anode current collector which comprises a Ni mesh, an Al foil, Ti, or stainless steel. 
   
   
       21 . The device of  claim 1 , wherein the electrolyte comprises a sodium containing salt with potassium, calcium, or magnesium containing salt or combination thereof solvated in water, and initially excludes lithium ions. 
   
   
       22 . The device of  claim 1 , wherein the electrolyte comprises Na 2 SO 4  solvated in water, and initially excludes lithium ions. 
   
   
       23 . The device of  claim 3 , wherein the active cathode electrode material has a formula A x M y O z , where A is Na or a mixture of Na and one or more of Li, K, Be, Mg, and Ca, x is within a range of 0 to 1.1, inclusive, before use and within a range of 0 to 10, inclusive, during use; M comprises any one or more transition metal, y is within a range of 1 to 3, inclusive, O is oxygen, and z is within a range of 2 to 7, inclusive. 
   
   
       24 . The device of  claim 23 , wherein y is within a range of 1.5 and 2.5, inclusive, and z is within a range of 3.5 to 4.5, inclusive. 
   
   
       25 . The device of  claim 24 , wherein the active cathode electrode material comprises a cubic spinel λ-manganate having a formula Li x Mn 2-z Al z O 4  where 1≦x<1.1 and 0≦z<0.1 before use, and Li x Na y Mn 2-z Al z O 4  where 0≦x<1.1, 0≦y<1, 0≦x+y<1.1, and 0≦z<0.1 in use. 
   
   
       26 . The device of  claim 25 , wherein the active cathode material electrode exhibits greater than or equal to about 75 mAh/g specific capacity with Na 2 SO 4  electrolyte. 
   
   
       27 . The device of  claim 26 , wherein the device exhibits a specific energy of greater than 20 Wh per kg of active cathode material when cycled between potentials of 0.60 and 1.9 V in 1 M Na 2 SO 4  at C/10 rate or slower. 
   
   
       28 . The device of  claim 26 , wherein the device comprises an activated carbon anode material, and exhibits a specific energy of between 10 and 105 Wh per kg of active cathode material for a specific power of between 20 to 1000 W per kg of active cathode material at 23° C. at 0.1 C rate. 
   
   
       29 . The device of  claim 28 , wherein the active cathode material exhibits a specific energy of between 30 and 50 Wh/kg at −5 to 23° C. at 1 C rate. 
   
   
       30 . The device of  claim 3 , wherein said active cathode electrode material has a formula A x M y O z , where A comprises at least 50 at % Na; M comprises any one or more transition metal; O is oxygen; x ranges from 3.5 to 4.5 before use and from 1 to 10 during use; y ranges from 8.5 to 9.5 and z ranges from 17.5 to 18.5. 
   
   
       31 . A method of operating hybrid aqueous energy storage device comprising an anode electrode, a cathode electrode, a separator, and a sodium containing aqueous electrolyte, the method comprising deintercalating alkali ions from an active cathode electrode material during initial charging of the device, reversibly intercalating sodium ions into the active cathode electrode material during discharge cycles, and deintercalating sodium ions from the active cathode electrode during subsequent charge cycles. 
   
   
       32 . The method of  claim 31 , wherein a cation concentration of the electrolyte is substantially constant during the discharge and charge cycles of the device. 
   
   
       33 . The method of  claim 31 , wherein the active cathode electrode material comprises a transition metal oxide, sulfide, phosphate, or fluoride. 
   
   
       34 . The method of  claim 33 , wherein the active cathode electrode material has a formula A x M y O z , where A comprises Na, M comprises any one or more transition metal; O is oxygen; x ranges from 0 to 1 before use and from 0 to 10 during use; y ranges from 1.5 to 2.5, and z ranges from 3.5 to 4.5. 
   
   
       35 . The method of  claim 34 , wherein A comprises Na during use and Li before the initial charging of the device and the active cathode electrode material is formed by providing lithium manganate cubic spinel material and then removing at least a portion of the lithium during the initial charging of the device to form a cubic spinel λ-manganate material. 
   
   
       36 . The method of  claim 35 , wherein the cubic spinel λ-manganate has a formula Li x Mn 2-z Al z O 4  where 1≦x<1.1 and 0≦z<0.1 before use, and Li x Na y Mn 2-z Al z O 4  where 0≦x<1.1, 0≦x<1, 0≦x+y<1.1, and 0≦z<0.1 in use. 
   
   
       37 . The method of  claim 36 , wherein the device exhibits a specific energy of greater than 20 Wh per kg of active cathode material when cycled between potentials of 0.60 and 1.9 V in 1 M Na 2 SO 4  at C/ 10  rate or slower. 
   
   
       38 . The method of  claim 36 , wherein the device comprises an activated carbon anode material, and exhibits a specific energy of between 10 and 105 Wh per kg of active cathode material for a specific power of between 20 to 1000 W per kg of active cathode material at 23° C. at 0.1 C rate. 
   
   
       39 . The method of  claim 38 , wherein the device exhibits a specific energy of between 40 and 60 Wh per kg of active cathode material at −5 to 23° C. at 1 C rate. 
   
   
       40 . The method of  claim 36 , wherein the device exhibits greater than or equal to about 75 mAh per gram of active cathode material specific capacity with Na 2 SO 4  electrolyte. 
   
   
       41 . The method of  claim 34 , wherein the anode electrode comprises porous activated carbon, graphite, mesoporous carbon, carbon nanotubes, disordered carbon, Ti-oxide material, V-oxide material, phospho-olivine material, mesoporous ceramic material or a composite thereof, and the electrolyte comprises Na 2 SO 4 , NaNO 3 , NaClO 4 , Na 3 PO 4 , Na 2 CO 3 , NaCl, NaOH, or combination thereof. 
   
   
       42 . The method of  claim 31 , wherein a charge containing electrochemical double layer is formed near the surface of an anode electrode during device charging, and the active charged species in this electrochemical double layer comprises Na ions, K ions, Ca ions, Li ions, or a combination thereof. 
   
   
       43 . The method of  claim 31 , wherein a partial charge transfer interaction occurs near the surface of a pseudocapacitive anode electrode during device charging, and the active charged species in this partial charge transfer interaction comprises Na ions, K ions, Ca ions, Li ions, or a combination thereof. 
   
   
       44 . The method of  claim 31 , wherein the active cathode electrode material does not intercalate or deintercalate electrolyte anions during the discharge and charge cycles. 
   
   
       45 . The method of  claim 43 , wherein the active cathode material only reversibly intercalates and deintercalates alkali cations and does not intercalate and deintercalate protons during the discharge and charge cycles. 
   
   
       46 . The method of  claim 31 , wherein the hybrid energy storage device operates between 5000 and 10000 cycles at full discharge with less than 20% loss of initial capacity. 
   
   
       47 . The method of  claim 31 , wherein the hybrid energy storage device comprises a Na 0.44 MnO 2 -type active cathode material exhibiting greater than or equal to about 20 mAh per gram of active cathode material specific capacity with a Na 2 SO 4  electrolyte. 
   
   
       48 . The method of  claim 31 , wherein the hybrid energy storage device comprises a Na 0.44 MnO 2 -type active cathode material, an activated carbon anode material, and exhibits a specific energy of greater than 20 Wh per kg active cathode material when cycled between potentials of 0.35 and 1.5 V in 1 M Na 2 SO 4  at C/5 rate or slower. 
   
   
       49 . The method of  claim 31 , wherein the hybrid energy storage device comprises a cathode electrode comprising doped or undoped Na 0.44 MnO 2  or λ-MnO 2  type active cathode material that supports greater than 1 kW of discharge power per kg of active cathode material. 
   
   
       50 . A secondary hybrid aqueous energy storage device comprising an anode electrode, a cathode electrode which is capable of reversibly intercalating at least one of sodium, potassium, calcium, or magnesium cations, a separator, and an aqueous electrolyte that comprises at least one of sodium, potassium, calcium, or magnesium cations, wherein the active cathode electrode material comprises a cubic spinel λ-manganate. 
   
   
       51 . The device of  claim 50 , wherein the cubic spinel λ-manganate has a formula Li x Mn 2-z Al z O 4  where 1≦x<1.1 and 0≦z<0.1 before use, and Li x Na y Mn 2-z Al z O 4  where 0≦x<1.1, 0≦x<1, 0≦x+y<1.1, and 0≦z<0.1 in use, and in use the cubic spinel λ-manganate reversibly intercalates at least one of sodium, potassium, calcium, or magnesium cations. 
   
   
       52 . The device of  claim 51 , wherein the active cathode electrode material is formed by providing a lithium manganate cubic spinel material and then removing at least a portion of the lithium during an initial charging of the device to form the cubic spinel λ-manganate material. 
   
   
       53 . The device of  claim 51 , wherein the anode electrode comprises a double-layer capacitor electrode which stores charge through a reversible nonfaradiac reaction of alkali metal cations on a surface of the anode electrode. 
   
   
       54 . The device of  claim 53 , wherein the anode electrode comprises porous activated carbon, graphite, mesoporous carbon, carbon nanotubes, disordered carbon, Ti-oxide material, V-oxide material, phospho-olivine material, mesoporous ceramic material, or a composite thereof, and the electrolyte comprises Na 2 SO 4 , NaNO 3 , NaClO 4 , Na 3 PO 4 , Na 2 CO 3 , NaCl, NaOH, or combination thereof. 
   
   
       55 . The device of  claim 50 , wherein the anode electrode comprises porous activated carbon, the electrolyte comprises Na 2 SO 4 , the cathode electrode contacts a cathode current collector and the anode electrode contacts an anode current collector. 
   
   
       56 . The device of  claim 50 , wherein the cathode electrode comprises 80 to 90% active cathode material, 0 to 10% conductive additive, and 0 to 10% binder material, and the anode electrode comprises 80 to 90% active anode material, 0 to 10% conductive additive, and 0 to 10% binder material. 
   
   
       57 . The device of  claim 56 , wherein the conductive additive comprises one or more of carbon black, graphite, a non-reactive metal, and a conductive polymer, and the binder comprises one or more of PTFE, PVC, cellulose-based material, PVDF, or other non-reactive non-corroding polymer material. 
   
   
       58 . The device of  claim 56 , wherein the binder material for one or more of the cathode electrode and anode electrode comprises hydrated birnessite. 
   
   
       59 . A method of making a secondary hybrid aqueous energy storage device, comprising:
 providing the energy storage device comprising an anode electrode, a cathode electrode which is capable of reversibly intercalating sodium cations, a separator, and a sodium cation containing aqueous electrolyte, wherein the active cathode electrode material comprises a cubic spinel lithium manganate; and   removing at least a portion of the lithium during an initial charging of the device to form a cubic spinel λ-manganate active cathode electrode material.   
   
   
       60 . The method of  claim 59 , wherein the anode electrode comprises a double-layer capacitor electrode which stores charge through a reversible nonfaradiac reaction of alkali metal cations on a surface of the anode electrode. 
   
   
       61 . The method of  claim 60 , wherein:
 the cubic spinel λ-manganate has a formula Li x Mn 2-z Al z O 4  where 1≦x<1.1 and 0≦z<0.1 before use, and Li x Na y Mn 2-z Al z O 4  where 0≦x<1.1, 0≦x<1, 0≦x+y<1.1, and 0≦z<0.1 in use;   the anode electrode comprises porous activated carbon, graphite, mesoporous carbon, carbon nanotubes, disordered carbon, Ti-oxide material, V-oxide material, phospho-olivine material, mesoporous ceramic material, or a composite thereof; and   the electrolyte comprises Na 2 SO 4 , NaNO 3 , NaClO 4 , Na 3 PO 4 , Na 2 CO 3 , NaCl, NaOH, or combination thereof.   
   
   
       62 . The method of  claim 61 , wherein the anode electrode comprises porous activated carbon, the electrolyte comprises Na 2 SO 4 , the cathode electrode contacts a cathode current collector and the anode electrode contacts an anode current collector. 
   
   
       63 . A secondary hybrid aqueous energy storage device, comprising: an anode electrode, a cathode electrode which is capable of reversibly intercalating potassium, calcium, or magnesium cations, a separator, and a potassium, calcium, or magnesium cation containing aqueous electrolyte, wherein an initial active cathode electrode material in the device comprises alkali containing active cathode electrode material which deintercalates alkali metal ions during initial charging of the device.