Electrode Materials For Rechargeable Zinc Cells and Batteries Produced Therefrom

Abstract

The present disclosure discloses a rechargeable Zn battery based on layered/tunnelled structure vanadium/molybdenum oxides, with/without the presence of neutral/cationic/anionic species and/or water molecules inserted into the interlayers/tunnels, of nano/microparticle morphology as robust materials for high rate and long term reversible Zn 2+ ion intercalation storage at the positive electrode, that are coupled with a metallic Zn negative electrode, and an aqueous electrolyte. The positive electrode may include electronically conducting additives and one or more binders along with the Zn 2+ intercalation material; the negative electrode is Zn metal in any form; the aqueous electrolyte is of pH 1 to 9 and contains a soluble zinc salt in a concentration range from 0.01 to 10 molar.

Therefore what is claimed is: 
     
         1 . A zinc ion battery, comprising:
 a positive electrode compartment having enclosed therein an intercalation layered positive electrode material M x V 2 O 5 .nH 2 O, wherein x is in a range from 0.05 to 1, n is in a range from 0 to 2, wherein M is any one or combination of a d-block metal ion, f-block metal ion and alkaline earth ion, the metal M ion being in a +2 to +4 valence state, and wherein said V 2 O 5  is a layered crystal structure having the metal ions M pillared between the layers, and waters of hydration coordinated to the metal ions M;   a negative electrode compartment having enclosed therein a negative electrode for storing zinc;   a separator electrically insulating and permeable to zinc ions separating the positive and negative compartments; and   an electrolyte comprising water and having a salt of zinc dissolved therein.   
     
     
         2 . The zinc ion battery according to  claim 1  wherein n is greater than 0 and less than 1. 
     
     
         3 . The zinc ion battery according to  claim 1  or  2  wherein some of the waters of hydration are hydrogen bonded to the layers. 
     
     
         4 . The zinc ion battery according to  claim 1 ,  2  or  3  wherein the negative electrode comprises zinc, and wherein the zinc ion battery is a zinc metal battery. 
     
     
         5 . The zinc ion battery according to  claim 1 ,  2 ,  3  or  4  wherein the electrolyte has a pH in a range from about 1 to about 8. 
     
     
         6 . The zinc ion battery according to any one of  claims 1  to  5  wherein the electrolyte has a pH in a range from about 4 to about 8. 
     
     
         7 . The zinc ion battery according to any one of  claims 1  to  6  wherein the intercalation layered cathode material has a nanostructured morphology which is defined by an average particle size of less than or equal to 1000 nm in at least one particle dimension. 
     
     
         8 . The zinc ion battery according to  claim 7  wherein the average particle size is less than 500 nm in a direction of Zn ion transport through the particle. 
     
     
         9 . The zinc ion battery according to any one of  claims 1  to  8  wherein the intercalation layered positive electrode material has a particulate morphology being particles having a mean size in a range from about 5 nm to about 50 μm. 
     
     
         10 . The zinc ion battery according to  claim 9  wherein the particles are coated with electrically conducting material. 
     
     
         11 . The zinc ion battery according to  claim 10  wherein the electrically conducting material is any one or combination of carbon powder and conducting polymer. 
     
     
         12 . The zinc ion battery according to  claim 9  wherein the particles are embedded in an electrically conducting matrix. 
     
     
         13 . The zinc ion battery according to  claim 12  wherein the electrically conducting matrix comprises any one or combination of carbon and conducting polymer, and including a binder. 
     
     
         14 . The zinc ion battery according to  claim 13  wherein the binder is any one or combination of styrene butadiene rubber (SBR), sodium carboxymethylcellulose (CMC), polyvinyl acetate (PVAc), polyethylene glycol (PEG), polybutyl acrylate (PBA), polyurethane, acrylonitrile, polypyrrole, polyaniline, polytetrafluoroethylene (PTFE), polyvinylidene fluoride (PVDF), perfluorosulfonic acid (PFSA), and poly(3,4-ethylenedioxythiophene) (PEDOT). 
     
     
         15 . The zinc ion battery according to any one of  claims 1  to  14  wherein the negative electrode comprises zinc metal. 
     
     
         16 . The zinc ion battery according to  claim 15  wherein the negative electrode is a zinc metal electrode. 
     
     
         17 . The zinc ion battery according to  claim 15  wherein the negative electrode is a zinc alloy. 
     
     
         18 . The zinc ion battery according to any one of  claims 1  to  14  wherein the negative electrode comprises a current collector, and a surface of the current collector facing into the negative electrode compartment having a layer of zinc bound thereto. 
     
     
         19 . The zinc ion battery according to  claim 18  wherein the layer of zinc comprises powdered zinc metal. 
     
     
         20 . The zinc ion battery according to  claim 18  wherein the layer of zinc comprises a sheet of zinc metal. 
     
     
         21 . The zinc ion battery according to  claim 18 ,  19  or  20  wherein the current collector is comprised on any one or combination of carbon, boron, lead, vanadium, chromium, manganese, iron, cobalt, nickel, cadmium, tungsten, bismuth, tin, indium, antimony, copper, titanium, and zinc metal. 
     
     
         22 . The zinc ion battery according to any one of  claims 1  to  14  wherein the negative electrode comprises a material that can store elemental zinc by any one or combination of intercalation, conversion, and capacitive storage. 
     
     
         23 . The zinc ion battery according to any one of  claims 1  to  22  wherein the electrolyte further comprises water dissolved zinc present in a range from about 0.01 to about 10 molar. 
     
     
         24 . The zinc ion battery according to any one of  claims 1  to  23  wherein the electrolyte further comprises water dissolved zinc present in a range from about 0.1 to about 4 M. 
     
     
         25 . The zinc ion battery according to  claim 23  wherein the salt of zinc comprises any one or combination of zinc sulfate, zinc acetate, zinc citrate, zinc iodide, zinc chloride, zinc perchlorate, zinc nitrate, zinc phosphate, zinc triflate, zinc bis(trifluoromethanesulfonyl)imide, zinc tetrafluoroborate, and zinc bromide. 
     
     
         26 . A zinc ion battery, comprising:
 a positive electrode compartment having enclosed therein and intercalated layered positive electrode material M x V 3 O 7 .nH 2 O, wherein x is in a range from 0.05 to 1, n is greater than 0 and less than 2, wherein M is any one or combination of a d-block metal ion, f-block metal ion and alkaline earth ion, the metal M ion being in a +2 to +4 valence state, and wherein said V 3 O 7  is a layered crystal structure having the metal ions M pillared between the layers, and waters of hydration coordinated to the metal ions M and/or hydrogen bonded to the layers;   a negative electrode compartment having enclosed therein a negative electrode for storing zinc;   a separator electrically insulating and permeable to zinc ions separating the positive and negative compartments; and   an electrolyte comprising water and having a salt of zinc dissolved therein.   
     
     
         27 . The material according to  claim 26  wherein n is greater than 0 and less than 1. 
     
     
         28 . The zinc ion battery according to  claim 26  or  27  wherein the negative electrode comprises zinc, and wherein the zinc ion battery is a zinc metal battery. 
     
     
         29 . The zinc ion battery according to  claim 26 ,  27 , or  28  wherein the electrolyte has a pH in a range from about 1 to about 8. 
     
     
         30 . The zinc ion battery according to any one of  claims 26  to  29  wherein the intercalation layered positive electrode material has nanostructured morphology which is defined by an particle size of less than or equal to 1000 nm in at least one particle dimension. 
     
     
         31 . The zinc ion battery according to  claim 30  wherein the average particle size is less than 500 nm in a direction of Zn ion transport through the particle. 
     
     
         32 . The zinc ion battery according to any one of  claims 26  to  30  wherein the intercalation layered positive electrode material has a particulate morphology being particles having a mean size in a range from about 5 nm to about 50 μm. 
     
     
         33 . The zinc ion battery according to  claim 32  wherein the particles are coated with an electrically conducting material. 
     
     
         34 . The zinc ion battery according to  claim 33  wherein the electrically conducting material is any one or combination of carbon powder and conducting polymer. 
     
     
         35 . The zinc ion battery according to  claim 32  wherein the particles are embedded in an electrically conducting matrix. 
     
     
         36 . The zinc ion battery according to  claim 35  wherein the electrically conducting matrix comprises any one or combination of carbon and conducting polymer, and including a binder. 
     
     
         37 . The zinc ion battery according to  claim 36  wherein the binder is any one or combination of styrene butadiene rubber (SBR), sodium carboxymethylcellulose (CMC), polyvinyl acetate (PVAc), polyethylene glycol (PEG), polybutyl acrylate (PBA), polyurethane, acrylonitrile, polypyrrole, polyaniline, polytetrafluoroethylene (PTFE), polyvinylidene fluoride (PVDF), perfluorosulfonic acid (PFSA), and poly(3,4-ethylenedioxythiophene) (PEDOT). 
     
     
         38 . The zinc ion battery according to any one of  claims 26  to  37  wherein the negative electrode comprises zinc metal. 
     
     
         39 . The zinc ion battery according to  claim 38  wherein the negative electrode is a zinc metal electrode. 
     
     
         40 . The zinc ion battery according to  claim 38  wherein the negative electrode is a zinc alloy. 
     
     
         41 . The zinc ion battery according to any one of  claims 26  to  37  wherein the negative electrode comprises a current collector, and a surface of the current collector facing into the negative electrode compartment having a layer of zinc bound thereto. 
     
     
         42 . The zinc ion battery according to  claim 41  wherein the layer of zinc comprises powdered zinc metal. 
     
     
         43 . The zinc ion battery according to  claim 41  wherein the layer of zinc comprises a sheet of zinc metal. 
     
     
         44 . The zinc ion battery according to  claim 41 ,  42  or  43  wherein the current collector is comprised of any one or combination of carbon, boron, lead, vanadium, chromium, manganese, iron, cobalt, nickel, cadmium, tungsten, bismuth, tin, indium, antimony, copper, titanium, and zinc metal. 
     
     
         45 . The zinc ion battery according to any one of  claims 26  to  37  wherein the negative electrode comprises a material that can store elemental zinc by any one or combination of intercalation, conversion, and capacitive storage. 
     
     
         46 . The zinc ion battery according to any one of  claims 26  to  45  wherein the electrolyte further comprises water dissolved zinc present in a range from about 0.01 to about 10 Molar. 
     
     
         47 . The zinc ion battery according to any one of  claims 26  to  46  wherein the electrolyte further comprises water dissolved zinc present in a range from about 0.1 to about 4 M. 
     
     
         48 . The zinc ion battery according to any one of  claims 26  to  47  wherein the salt of zinc comprises any one or combination of zinc sulfate, zinc acetate, zinc citrate, zinc iodide, zinc chloride, zinc perchlorate, zinc nitrate, zinc phosphate, zinc triflate, zinc bis(trifluoromethanesulfonyl)imide, zinc tetrafluoroborate, and zinc bromide. 
     
     
         49 . A zinc ion battery; comprising:
 a positive electrode compartment having enclosed therein an intercalated layered positive electrode material M x MoO y .nH 2 O, wherein x is in a range from 0 to 1, y is in a range from 2 to 3, n is in a range from 0 to 2, wherein M is any one or combination of a d-block metal ion, f-block metal ion and alkaline earth ion, the metal M ion being in a +2 to +4 valence state, and wherein said MoO y  has a layer or tunnel crystal structure, and the metal ions M, if present, pillared between the layers, and waters of hydration coordinated to the metal ions M pillared between the layers;   a negative electrode compartment having enclosed therein a negative electrode for storing zinc;   a separator electrically insulating and permeable to zinc ions separating the positive and negative compartments; and   an electrolyte comprising water and having a salt of zinc dissolved therein.   
     
     
         50 . The zinc ion battery according to  claim 49  wherein the negative electrode comprises zinc, and wherein the zinc ion battery is a zinc metal battery. 
     
     
         51 . The zinc ion battery according to  claim 49  or  50  wherein the electrolyte has a pH in a range from about 1 to about 8. 
     
     
         52 . The zinc ion battery according to any one of  claims 49  to  51  wherein the electrolyte has a pH in a range from about 4 to about 8. 
     
     
         53 . The zinc ion battery according to any one of  claims 49  to  52  wherein the intercalation layered positive electrode material has nanostructured morphology which is defined by a particle size of less than or equal to 1000 nm in at least one particle dimension. 
     
     
         54 . The zinc ion battery according to  claim 53  wherein the average particle size is less than 500 nm in a direction of Zn ion transport through the particle. 
     
     
         55 . The zinc ion battery according to any one of  claims 49  to  54  wherein the intercalation layered positive electrode material has a particulate morphology being particles having a mean size in a range from about 5 nm to about 50 μm. 
     
     
         56 . The zinc ion battery according to  claim 55  wherein the particles are coated with electrically conducting material. 
     
     
         57 . The zinc ion battery according to  claim 56  wherein the electrically conducting material is any one or combination of carbon powder and conducting polymer. 
     
     
         58 . The zinc ion battery according to  claim 55  wherein the particles are embedded in an electrically conducting matrix. 
     
     
         59 . The zinc ion battery according to  claim 58  wherein the electrically conducting matrix comprises any one or combination of carbon and conducting polymer, and including a binder. 
     
     
         60 . The zinc ion battery according to  claim 59  wherein the binder is any one or combination of styrene butadiene rubber (SBR), sodium carboxymethylcellulose (CMC), polyvinyl acetate (PVAc), polyethylene glycol (PEG), polybutyl acrylate (PBA), polyurethane, acrylonitrile, polypyrrole, polyaniline, polytetrafluoroethylene (PTFE), polyvinylidene fluoride (PVDF), perfluorosulfonic acid (PFSA), and poly(3,4-ethylenedioxythiophene) (PEDOT). 
     
     
         61 . The zinc ion battery according to any one of  claims 49  to  60  wherein the negative electrode comprises zinc metal. 
     
     
         62 . The zinc ion battery according to  claim 61  wherein the negative electrode is a zinc metal electrode. 
     
     
         63 . The zinc ion battery according to  claim 61  wherein the negative electrode is a zinc alloy. 
     
     
         64 . The zinc ion battery according to any one of  claims 49  to  60  wherein the negative electrode comprises a current collector, and a surface of the current collector facing into the negative electrode compartment having a layer of zinc bound thereto. 
     
     
         65 . The zinc ion battery according to  claim 64  wherein the layer of zinc comprises powdered zinc metal. 
     
     
         66 . The zinc ion battery according to  claim 64  wherein the layer of zinc comprises a sheet of zinc metal. 
     
     
         67 . The zinc ion battery according to  claim 64 ,  65  or  66  wherein the current collector is comprised on any one or combination of carbon, boron, lead, vanadium, chromium, manganese, iron, cobalt, nickel, cadmium, tungsten, bismuth, tin, indium, antimony, copper, titanium, and zinc metal. 
     
     
         68 . The zinc ion battery according to any one of  claims 49  to  67  wherein the negative electrode comprises a material that can store elemental zinc by any one or combination of intercalation, conversion, and capacitive storage. 
     
     
         69 . The zinc ion battery according to any one of  claims 49  to  68  wherein the electrolyte further comprises water said dissolved zinc present in a range from about 0.01 to about 10 molar. 
     
     
         70 . The zinc ion battery according to any one of  claims 49  to  69  wherein the electrolyte further comprises water said dissolved zinc present in a range from about 0.1 to about 4 M. 
     
     
         71 . The zinc ion battery according to any one of  claims 49  to  70  wherein the salt of zinc comprises any one or combination of zinc sulfate, zinc acetate, zinc citrate, zinc iodide, zinc chloride, zinc perchlorate, zinc nitrate, zinc phosphate, zinc triflate, zinc bis(trifluoromethanesulfonyl)imide, zinc tetrafluoroborate, and zinc bromide. 
     
     
         72 . The zinc ion battery according to any one of  claims 49  to  71  wherein n is greater than 0 and less than 2. 
     
     
         73 . The zinc ion battery according to any one of  claims 49  to  72  wherein some of the waters of hydration are hydrogen bonded to the layers.