LITHIUM ION BATTERY AND CAPACITOR HYBRIDIZATION IN MATERIAL AND ELECTRODE LEVEL

Abstract

At least one of the anode and cathode of a lithium-ion processing electrochemical cell are prepared with a layer of mixed partides of both active lithium battery electrode materials and lithium ion adsorbing capacitor materials, or with co-extensive, contiguous layers of battery electrode particles in one layer and capacitor particles in the adjoining layer. The proportions of active battery electrode particles and active capacitor particles in one or both of the electrodes are predetermined to provide specified energy density (Wh/kg) and power density (W/kg) properties of the cell for its intended application.

Claims

1. An electrochemical cell comprising an anode, a cathode, and an electrolyte solution containing a lithium electrolyte salt dissolved in a non-aqueous liquid solvent in which the electrolyte salt produces lithium cations and associated anions; the electrochemical cell being further characterized in that; the anode and cathode of the electrochemical cell each contain a layer of resin-bonded particles of an electrode material bonded to at least one side of a current collector foil, the resin-bonded electrode material particles being capable of intercalating lithium from the electrolyte solution and de-intercalating lithium into the electrolyte solution so that such electrode material particles in the anode and cathode can function as a lithium-ion battery cell; and at least one of the anode and cathode of the electrochemical cell also containing particles of an electrode material that are capable of adsorbing lithium cations from the electrolyte solution and desorbing lithium cations into the electrolyte solution to function as a capacitor, such electrode material capacitor particles being mixed with the battery electrode material particles in the same electrode resin-bonded layer or being formed in a separate porous layer, coextensive and lying against a layer of battery electrode particles, the combination of the amounts and proportions of battery particles and capacitor particles present in the anode and the cathode each providing equal electrochemical capacities in ampere-hours at each electrode, the amounts and proportions of battery particles and capacitor particles in the anode and/or cathode further being predetermined to provide a specified hybridized energy density (Wh/kg) and power density (W/kg) for the electrochemical cell.

2. An electrochemical cell as stated in claim 1 in which the anode and cathode of the electrochemical cell each contain a combination of battery particles and capacitor particles as an electrode material resin-bonded to the respective current collector foils.

3. An electrochemical cell as stated in claim 1 in which only one of the anode and cathode of the electrochemical cell contains a combination of battery particles and capacitor particles as an electrode material resin bonded to the anode or cathode current collector foil.

4. An electrochemical cell as stated in claim 1 in which a mixture of battery electrode material particles and capacitor electrode material particles are applied as a single porous resin-bonded electrode layer to one or both of the anode and cathode current collectors.

5. An electrochemical cell as stated in claim 1 in which separate, porous, adjacent, coextensive layers of battery electrode material particles and capacitor electrode material particles are applied to at least one side of a current collector foil for an anode of cathode of the cell.

6. An electrochemical cell as stated in claim 1 in which the anode and cathode of the electrochemical cell each contain battery particles and capacitor particles and the adsorption capacity of capacitor particles in the anode is equivalent to the adsorption capacity of the capacitor particles in the cathode such that the electrochemical cell functions as both a lithium-ion battery and a capacitor.

7. An electrochemical cell as stated in claim 1 in which the anode and cathode of the electrochemical cell each contain battery particles and capacitor particles and the adsorption capacity of the capacitor particles in the cathode is less than the adsorption capacity of the capacitor particles in the anode such that the electrochemical cell functions as a lithium-ion battery, a lithium ion capacitor, and a capacitor.

8. An electrochemical cell as stated in claim 1 in which the anode and cathode of the electrochemical cell each contain battery particles and capacitor particles and the adsorption capacity of the capacitor particles in the anode is less than the adsorption capacity of the capacitor particles in the cathode such that the electrochemical cell functions as a lithium-ion battery, a lithium ion capacitor, and a capacitor.

9. An electrochemical cell as stated in claim 1 in which the anode and cathode of the electrochemical cell each contain battery particles but only the anode contains capacitor particles such that the electrochemical cell functions as a lithium-ion battery and lithium ion capacitor.

10. An electrochemical cell as stated in claim 1 in which the anode and cathode of the electrochemical cell each contain battery particles and capacitor particles but only the cathode contains capacitor particles such that the electrochemical cell functions as a lithium-ion battery and lithium ion capacitor.

11. A method of forming at least one of an anode and cathode for an electrochemical cell comprising an anode, a cathode, and an electrolyte solution containing a lithium electrolyte salt dissolved in a non-aqueous liquid solvent in which the electrolyte salt produces lithium cations and associated anions; the method comprising: applying particles of active anode material as a porous layer of anode material to at least one side of an anode current collector foil for the electrochemical cell, the particles of active anode material being composed for intercalating and de-intercalating lithium ions from the lithium ion containing electrolyte solution so that that such electrode material particles can function as a lithium-ion battery cell; applying particles of active cathode material as a porous layer of cathode material to at least one side of a cathode current collector foil, the particles of active cathode material being composed for intercalating and de-intercalating lithium ions from the lithium ion containing electrolyte solution; and also applying particles of an active electrode material, which are composed to adsorp lithium ions from the electrolyte solution and desorp lithium ions into the electrolyte solution in the nature of a capacitor, to at least one of the anode current collector foil and cathode current collector foil, the combination of the amounts and proportions of battery particles and capacitor particles in the anode and the cathode each providing equal electrochemical capacities in ampere-hours, the amounts and proportions of battery particles and capacitor particles in the anode and/or cathode further being predetermined to provide a specified hybridized energy density (Wh/kg) and power density (W/kg) for the electrochemical cell.

12. A method of forming at least one of an anode and cathode for an electrochemical cell as stated in claim 11 in which a combination of battery particles and capacitor particles are applied to each of the current collector foils for the anode and cathode of the electrochemical cell.

13. A method of forming at least one of an anode and cathode for an electrochemical cell as stated in claim 11 in which a combination of battery particles and capacitor particles are applied to only one of the current collector foils for the anode and cathode of the electrochemical cell.

14. A method of forming at least one of an anode and cathode for an electrochemical cell as stated in claim 11 in which a mixture of battery electrode material particles and capacitor electrode material particles are applied as a single porous resin-bonded electrode layer to one or both of the anode and cathode current collectors.

15. A method of forming at least one of an anode and cathode for an electrochemical cell as stated in claim 11 in which separate, porous overlying, coextensive layers of battery electrode material particles and capacitor electrode material particles are applied to at least one side of a current collector foil for an anode of cathode of the cell.

16. A method of forming at least one of an anode and cathode for an electrochemical cell as stated in claim 11 in which battery particles and capacitor particles are applied to each of the anode and cathode current collectors, and the adsorption capacity of capacitor particles in the anode is equivalent to the adsorption capacity of the capacitor particles in the cathode such that the electrochemical cell functions as both a lithium-ion battery and a capacitor.

17. A method of forming at least one of an anode and cathode for an electrochemical cell as stated in claim 11 in which battery particles and capacitor particles are applied to each of the anode and cathode current collectors and the adsorption capacity of the capacitor particles in the cathode is less than the adsorption capacity of the capacitor particles in the anode such that the electrochemical cell functions as a lithium-ion battery, a lithium ion capacitor, and a capacitor.

18. A method of forming at least one of an anode and cathode for an electrochemical cell as stated in claim 11 in which battery particles and capacitor particles are applied to each of the anode and cathode current collectors and the adsorption capacity of the capacitor particles in the anode is less than the adsorption capacity of the capacitor particles in the cathode such that the electrochemical cell functions as a lithium-ion battery, a lithium ion capacitor, and a capacitor.

19. A method of forming at least one of an anode and cathode for an electrochemical cell as stated in claim 11 in which battery particles are applied to each of the anode and cathode current collectors but capacitor particles are applied only to the anode such that the electrochemical cell functions as a lithium-ion battery and a lithium ion capacitor.

20. A method of forming at least one of an anode and cathode for an electrochemical cell as stated in claim 11 in which battery particles are applied to each of the anode and cathode current collectors but capacitor particles are applied only to the cathode such that the electrochemical cell functions as a lithium-ion battery and a lithium ion capacitor.

Description

BRIEF DESCRIPTION OF THE DRAWINGS

[0041] FIG. 1 is a schematic, cross-sectional side view of an anode current collector foil coated on both major sides with a mixture of active material particles for a lithium-ion battery anode and a capacitor anode, a cathode current collector foil coated on both sides with a mixture of active material particles for a lithium-ion battery cathode and a capacitor cathode. The two electrodes are rectangular in shape (not visible in the side view of FIG. 1). The opposing major faces of the anode and cathode are physically separated by porous rectangular polymer separator layer wound from the full outer surface of the cathode, around one edge of the cathode to fully cover the inner face of the cathode and separate it from the adjoining face of the anode, around the edge of the anode to cover the outer face of the anode. The two electrodes with their hybrid electrode materials are placed within a closely spaced pouch container. The pouch contains a non-aqueous electrolyte solution which permeates and fills the pores of the separator and of the respective active anode and cathode coating layers. The respective current collector foils have uncoated tabs extending up from their top sides and through the top surface of the pouch container.

[0042] FIG. 2 is a schematic oblique view of a porous layer of intermixed particles of battery electrode material, capacitor electrode material, and conductive carbon bonded to both major surfaces of a rectangular current collector foil. The respective electrode materials may be a mixture of particles of lithium-ion battery cathode materials and capacitor cathode materials bonded to an aluminum foil. The particles of the two opposing layers are resin-bonded to each other and each layer is resin-bonded to a surface of the current collector. The current collector has an uncoated tab extending from one of its sides for connection to another hybrid electrode.

[0043] FIG. 3 is a schematic oblique view of a porous layer of, for example, particles of lithium-ion battery NMC cathode particles mixed with conductive carbon particles bonded to both major surfaces of a rectangular current collector foil. And a coextensive porous layer of capacitor cathode particles mixed with conductive carbon particles is resin bonded to the outer surfaces of the battery cathode layers. The current collector has an uncoated tab extending from one of its sides for connection to another hybrid electrode.

DESCRIPTION OF PREFERRED EMBODIMENTS

[0044] In accordance with practices of this invention, one or both of the anode and cathode of an electrochemical cell are formed with a mixture of compatible and complementary particulate electrode materials suitable for a lithium-ion battery and for a capacitor in which the electrode functions by intercalating/de-intercalating and adsorbing and desorbing lithium cations and associated anions from a non-aqueous electrolyte solution. When both the anode and cathode of a cell both contain suitable lithium-ion battery materials and capacitor materials in predetermined proportions, the power and energy performance of the electrochemical cell may be balanced for specific application for which the cell is intended.

[0045] When one of the anode or cathode contains a predetermined hybrid mixture of particulate active battery and capacitor materials, the performance of the battery is modified.

[0046] A further listing of anode and cathode materials for lithium batteries includes:

[0047] Suitable battery cathode materials include:

[0048] LixMO.sub.2 (M=Co, Ni, Mn, Cr, V),

[0049] LixM.sub.2O.sub.4 (M=Co, Ni, Mn, Cr, V),

[0050] LixNiyM.sub.1-yO.sub.2 (M=Fe, Mn),

[0051] LiNi.sub.1-x-y-zCoxM.sub.1-yM.sub.2zO.sub.2 (M.sub.1, M.sub.2=Al, Ni, Co, Fe, Mn, V, Cr, Ti, W, Ta, Mo),

[0052] LiMn.sub.2-xM.sub.xO.sub.4 (M=Co, Ni, Fe, Cu, Cr, V),

[0053] LiNiVO.sub.4, LiNbO.sub.3, LiFePO.sub.4, LiTi.sub.2(PO.sub.4).sub.3, Li.sub.3V.sub.2(PO.sub.4).sub.3, LiMPO.sub.4 (M-Ti, Ge, Zr, Hf), Li.sub.3FeV(PO.sub.4).sub.3, LiFeNb(PO.sub.4).sub.3, Li.sub.2FeNb(PO.sub.4).sub.3, LixFeyMn.sub.1-yPO.sub.4, LiMSiO.sub.4 (M=Mn, Fe), LixFe.sub.2(WO.sub.4).sub.3, LixFe.sub.2(SO.sub.4).sub.3, and LiFeO.sub.2.

[0054] Suitable battery anode materials include:

[0055] Forms of carbon: graphite, MCMB, hard carbon, soft carbon, activated carbon, amorphous carbon.

[0056] Metals: Si, Sn, Sb, Ge, Pb.

[0057] Metal alloys: FeSn.sub.2, Co.sub.3Sn.sub.2, CoSn, CoSn.sub.2, Ni.sub.3Sn.sub.2, Ni.sub.3Sn.sub.4, Mg.sub.2Sn, Co.sub.xCu.sub.6-xSn.sub.5(0x2), SnMx (M=Sb, Cd, Ni, Mo, Fe), MSi.sub.2 (M=Fe, Co, Ca, Ni), Cu.sub.2Sb, CoSb.sub.2, FeSb.sub.2, Zn.sub.4Sb.sub.3, CoSb.sub.3, CoFe.sub.3Sb.sub.12, InSb, etc.

[0058] Metal oxides: MOx (M=Sn, Si, Pb, Ge, Co, Ni, Cu, Fe, Pd, Cr, Mo, W, Nb), CaSnO.sub.3, Al.sub.2(MoO.sub.4).sub.3, etc.

[0059] Lithium metal oxide: Li.sub.4Ti.sub.5O.sub.12, LiTi.sub.2O.sub.4, LiTi.sub.2(PO.sub.4).sub.3, etc.

[0060] Metal sulfide: TiS.sub.2, MoS.sub.2, etc.

[0061] Metal nitride: M.sub.3N (M=Fe, Co, Cu, Ni), M.sub.3N.sub.4 (M=Sn, Ge), Zn.sub.3N.sub.2, CrN, VN, CrxFe(.sub.1-x)N, Li.sub.3FeN.sub.2, Li.sub.3-xMxN (M=Co, Ni, Fe, Cu), Li.sub.7MnN.sub.4, etc.

[0062] Metal carbide: SiC, TiC, etc.

[0063] Metal phosphide: VP.sub.2, ZnP.sub.2, FeP.sub.2, CoP.sub.3, MnP.sub.4, CrP, Sn.sub.4P.sub.3, Ni.sub.2P, etc.

[0064] Polymers: polypyrrole, polyaniline, etc.

[0065] A substantial listing of lithium-adsorbing capacitor materials for the hybrid anode and cathode mixtures has been presented above in this specification.

[0066] The particulate battery and capacitor electrode materials may be mixed and bonded to a current collector as a single hybrid anode or cathode layer. Or they may be applied as separate battery and capacitor material layers on a current collector. The active battery and capacitor electrode materials are prepared in the form of micrometer-size particles, mixed with like-sized particles of conductive carbon. Conductive carbons have different particle sizes based on different sources of the carbon. For example, some conductive carbons are nanometer size (Super P) and some are micrometer-size (KS6). The electrode material particles and conductive carbon particles are coated with a suitable polymeric binder resin such as polyvinylidene difluoride (PVDF) for the formation of the porous layers of electrode materials on the current collectors. The preparation of the hybrid anode and cathode layers is described in detail below in this specification.

[0067] The respective electrode members are often formed as rectangular sheets or layers and assembled as intermixed cathodes and anodes in a stacked assembly. Each anode is separated from a facing cathode by an interposed separator. This may be accomplished, for example, by the use of a relatively long, porous, polypropylene separator sheet that is wound back and forth between each facing surface of a layer of anode structure and cathode structure. An assembled structure of a predetermined number of one or more paired anode-cathode cells is paced in a closely fitting pouch or other suitable container. The pores of the separator layers and the alternating anode and cathode layers are infiltrated with a suitable non-aqueous solution of a lithium salt, the solution containing a predetermined amount of lithium cations and associated anions.

[0068] The common electrolyte for the subject hybridized electrochemical cell may be a suitable lithium salt dissolved in one or more organic liquid solvents. Examples of salts include lithium bis(oxalate)borate (LiBOB), lithium oxalyldifluoroborate (LiODFB), lithium fluoroalkylphosphate (LiFAP), lithium hexafluoroarsenate (LiPF.sub.6), lithium hexafluoroarsenate (LiAsF.sub.6), lithium tetrafluoroborate (LiBF.sub.4), lithium perchlorate (LiClO.sub.4), lithium trifluoromethanesulfonate (LiCF.sub.3SO.sub.3), lithium trifluoroethanesulfonimide (LiTFESI), lithium bis(fluorosulfonyl)imide (LiFSI), lithium bis-trifluoromethanesulfonimide (LiTFMSI), and the like. Some examples of solvents that may be used to dissolve the electrolyte salt include ethylene carbonate, dimethyl carbonate, methylethyl carbonate, and propylene carbonate. There are other lithium salts that may be used and other solvents. But a combination of lithium salt and non-aqueous liquid solvent is selected for providing suitable mobility and transport of lithium ions between the opposing electrodes in the operation of both electrode compositions of the hybrid battery/capacitor electrochemical cell. And the lithium salt is capable of forming a suitable amount of cations and anions in the electrolyte solution for operation of both electrodes of the hybrid electrode materials of either or both of the hybrid electrode compositions.

[0069] The nonaqueous electrolyte solution is carefully dispersed into and between closely spaced layers of the electrode elements and separator layers of each electrode of the hybrid cell.

[0070] The porous separator may be formed of a porous film or of porous interwoven fibers of suitable polymer material, or of ceramic particles, or a polymer material filled with ceramic particles. Suitable polymer materials include, for example, porous films or layers of polyethylene, polypropylene, and poly (ethylene-propylene). In the assembly of the hybrid electrodes, the porous separator layer is filled with a liquid lithium-ion containing electrolyte and enables the transport of lithium ions between the porous electrode members. But the separator layer is used to prevent direct electrical contact between each of the negative and positive electrode material layers in each unit, and is shaped and sized to serve this function.

[0071] FIG. 1 presents a simplified, schematic, cross-sectional side view of an assembly of a single cell 12 of hybrid lithium-ion battery and lithium-ion adsorbing capacitor electrode materials assembled into a polymer-coated, aluminum foil pouch 16. The cell 12 with hybrid electrode materials comprises a cathode current collector foil 18 coated on both major sides with a porous layer of a mixture of active material particles 20 for a lithium-ion battery cathode and a capacitor cathode. Cell 12 also comprises an anode current collector foil 22 coated on both sides with a porous layer mixture of active material particles 24 for a lithium-ion battery anode and a capacitor anode. The two electrodes are rectangular in shape (not visible in the side view of FIG. 1). The opposing major faces of the anode and cathode are physically separated by porous rectangular polymer separator layer 26 which may be wound from the full outer surface of the cathode, around one edge of the cathode to separate the adjoining face of the anode and the cathode, around the edge of the anode to cover the outer face of the anode. The two electrodes with their hybrid electrode materials are placed within a closely spaced pouch container 16. The pouch 16 contains a non-aqueous electrolyte solution 14 which permeates and fills the pores of the separator and of the respective active anode and cathode coating layers 20, 24. The respective current collector foils 18, 22 have uncoated tabs 18, 22 extending up from their top sides and through the top surface of the pouch container 16.

[0072] As illustrated in FIG. 1, the hybrid mixtures of cathode material 20 and anode material 24 were each prepared as single layers of intermixed lithium-ion battery electrode material particles and lithium cation adsorbing capacitor materials which were bonded as substantially uniformly thick layers of resin-bonded particles on each main surface of the respective current collectors 18, 22. The connector tab portions 18, 22 of the current collector foils 18, 22 are not coated with electrode material. The hybrid electrode materials may be prepared in either of two processes. The processes will be illustrated using lithium battery cathode material and capacitor cathode material. But the processes are essentially the same on the preparation of anode materials.

[0073] A suitable lithium battery cathode material is selected, such as micrometer-size particles of lithium nickel manganese cobalt oxide (LiNiMnCoO.sub.2, NMC). And suitable capacitor cathode material is selected, such as particles of activated carbon. The atomic or molecular proportions of the cathode materials are determined to provide a desired hybrid battery/capacitor effect in the cathode as well as in the anode of the cell. In a first process, the proportioned amount of the respective cathode particles are mixed and blended with each other and with a suitable (but, typically, a relatively smaller amount) of conductive carbon particles to enhance the electron conductivity of the finished cathode. The blended particle mixture may then be mixed as a slurry in a solution or dispersion of a polymer binder material. The binder may, for example be polyvinylidene difluoride polymer dissolved in NMP. The blended cathode particles and conductive carbon particles are mixed and slurried in the binder solution. The wet mixture is then carefully spread, in one or more applications, as a thin porous layer onto one or both of the intended surfaces of a suitable current collector foil, for example an aluminum current collector foil. The solvent, or liquid dispersant, is evaporated, or otherwise removed, to leave the porous layer of particles, resin-bonded to each other and to the surface of the metallic current collector foil.

[0074] FIG. 2 is a side, elevational view of an illustrative cathode having a porous layer 220 of a hybrid mixture battery cathode material and capacitor cathode material deposited on both major faces of an aluminum current collector foil 218. As described with respect to FIG. 1, the overall hybrid electrode may have a rectangular shape. The thickness of the current collector foil is typically in the range of about five to fifteen micrometers and the thickness of the porous layers of hybrid cathode material is in the range of about fifty to one hundred-fifty micrometers.

[0075] In a second process, the particles of cathode battery material and the particles of capacitor material are deposited separately to form two distinct porous layers, one porous layer preferably co-extensively overlying a first deposited layer, of porous electrode materials on a current collector foil. As illustrated in the side elevational view of FIG. 3, a first porous layer 320 of resin-bonded battery cathode particles is formed and bonded to each surface of current collector foil 318. A separately formed layer of capacitor cathode particles applied as a co-extensive porous resin bonded layer 321 to the outer surfaces of each first layer 320 of battery cathode particles. The separate layers of battery particles and capacitor particles may be applied in either or to both sides of the current collector or in reverse orders on opposing sides of the current collector. The total thickness of the two layers 320, 321 may be in the above specified range. But the thicknesses of the individual layers may vary depending on the intended proportions of their content in the electrode.

[0076] As stated in the Summary section of this specification, the object of this invention is to form a lithium ion based electrochemical cell in which the anode and cathode electrodes comprise active lithium battery electrode material particles in each of the anode and cathode. And at least one of the anode and cathode also contain particles of capacitor material particles which are composed to adsorb and desorp lithium ions that are in a surrounding lithium electrolyte solution. The compositions and amounts of the active materials of the two electrodes are such that the electrochemical capacities of the anode and cathode are balanced. But the respective proportions of battery and capacitor materials may be varied such that the function of the resulting hybrid cell and be varied from that of a lithium-ion battery and capacitor (LIB+CAP) or to a lithium ion battery, capacitor and lithium ion capacitor (LIB+CAP+LIC) or to a lithium ion battery and lithium ion capacitor (LIB+LIC).