SOLID-STATE BATTERY HAVING AN ELECTRODE COMPRISING OF AN ELECTRONICALLY CONDUCTIVE POLYMER
20210050596 ยท 2021-02-18
Inventors
- Zhe LI (Shanghai, CN)
- Haijing LIU (Shanghai, CN)
- Yong LU (Shanghai, CN)
- Mengyan HOU (Shanghai, CN)
- Deween Kong (Shanghai, CN)
Cpc classification
H01M4/62
ELECTRICITY
H01M4/485
ELECTRICITY
H01M50/40
ELECTRICITY
H01M4/131
ELECTRICITY
Y02E60/10
GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
H01M10/0525
ELECTRICITY
International classification
H01M4/62
ELECTRICITY
H01M10/0525
ELECTRICITY
H01M4/131
ELECTRICITY
Abstract
A solid-state battery cell for a lithium ion battery is disclosed. The battery cell includes a first electrode; a second electrode; and an ionically conductive layer sandwiched between the first electrode and the second electrode. At least one of the first electrode and the second electrode includes an electronically conductive polymer (ECP). The at least one of the first electrode and the second electrode comprises about 20-98 weight percent (wt %) of an active material, about 0.1-30 wt % of the ECP, and about 5-70 wt % of an ionically conductive material that includes one or more of a solid-state electrolyte (SSE) material and a lithium salt.
Claims
1. A battery cell, comprising: a first electrode; a second electrode; and an ionically conductive layer sandwiched between the first electrode and the second electrode; wherein at least one of the first electrode and the second electrode, comprises an electronically conductive polymer (ECP).
2. The battery cell of claim 1, wherein the ECP comprises a -conjugated polymeric chain.
3. The battery cell of claim 2, wherein the ECP comprises at least one of a polypyrrole (PPy), a polyaniline (PANI), a polythiophene (PT), a poly(3,4-ethylenedioxy thiophene) (PEDOT), a poly(3,4-propylenedioxy thiophene) (PProDOT), PEDOT:poly(4-styrene sulfonate) (PEDOT:PSS), polyacetylene (PA), a poly(p-phenylenevinylene) (PPV), and a poly(3-hexylthiophene)
4. The battery cell of claim 1, further comprising a separator interlayer in direct intimate contact with the ionically conductive layer and one of the first electrode and the second electrode.
5. The battery cell of claim 1, wherein the at least one of the first electrode and the second electrode, further comprises a solid-state electrolyte material.
6. The battery cell of claim 5, wherein the solid-state electrolyte (SSE) material comprises at least one of a sulfide-based SSE including a Li.sub.2SP.sub.2S.sub.5 system and lithium argyrodite Li.sub.6PS.sub.5X, wherein X=Cl, Br, or I; an oxide-based SSE including Li.sub.7La.sub.3Zr.sub.2O.sub.12; a polymer-based SSE including a polyethylene oxide (PEO) with LiTFSI, a nitride-based SSE including a LiSi.sub.2N.sub.3; a hydride-based SSE including LiBH.sub.4LiNH.sub.2; a halide-based SSE including Li.sub.3OCl, a borate-based SSE including Li.sub.2OB.sub.2O.sub.3P.sub.2O.sub.5; an inorganic SSE/polymer-based hybrid electrolyte including Li.sub.7La.sub.3Zr.sub.2O.sub.12/polyvinylidene fluoride (PVDF)/Li salt hybrid solid electrolyte; and a surface-modified SSE including Indium (In)-deposited Li.sub.7La.sub.3Zr.sub.2O.sub.12.
7. The battery cell of claim 6, further comprising a liquid electrolyte permeating the first anode, the ionically conductive layer, and the second anode.
8. The battery cell of claim 1, wherein the at least one of the first electrode and the second electrode comprises from about 20 weight percent (wt %) to about 98 wt % of an active material, from about 0.1 wt % to about 30 wt % of the ECP, and from about 5 wt % to about 70 wt % of a solid-state electrolyte (SSE) material.
9. The battery cell of claim 1, wherein the at least one of the first electrode and the second electrode comprises from about 20 weight percent (wt %) to about 98 wt % of an active material, from about 0.1 wt % to about 30 wt % of the ECP, and from about 5 wt % to about 70 wt % of a lithium salt.
10. The battery cell of claim 9, wherein the lithium salt comprises a lithium cation and at least one of a hexafluoroarsenate; a hexafluorophosphate; a tris(pentafluoroethyl)-trifluorophosphate (FAP); a perchorate; a tetrafluoroborate; a trifluoromethanesulfonate (Triflate); a bis(fluorosulfonyl)amide (FSI); a cyclo-difluoromethane-1,1-bis(sulfonyl)imide (DMSI); cyclo-difluoromethane-1,1-bis(sulfonyl)imide (HPSI); a bis(trifluoromethanesulfonyl)imide (TFSI); a bis(perfluoroethanesulfonyl)imide (BETI), a bis(oxalate)borate (BOB); a difluoro(oxalato)borate (DFOB); a bis(fluoromalonato)borate (BFMB); a tetracyanoborate (Bison); a dicyanotriazolate (DCTA), a dicyano-trifluoromethyl-imidazole (TDI); and a dicyano-pentafluoroethyl)-imidazole (PDI).
11. An electrode comprising: an electrode layer having: from about 20 weight % (wt %) to about 98 wt % of an electrode active material; from about 5 wt % to about 70 wt % of an ionically conductive material; and from about 0.1 wt % to about 30 wt % of an electronically conductive polymer.
12. The electrode of claim 11, wherein the electronically conductive polymer comprises at least one of a polypyrrole (PPy), a polyaniline (PANI), a polythiophene (PT), a poly(3,4-ethylenedioxy thiophene) (PEDOT), a poly(3,4-propylenedioxy thiophene) (PProDOT) and a PEDOT:poly(4-styrene sulfonate) (PEDOT:PSS), a polyacetylene (PA), a poly(p-phenylenevinylene) (PPV), and a poly(3-hexylthiophene).
13. The electrode of claim 12, wherein the electrode active material comprises a lithium transition-metal oxide.
14. The electrode of claim 12, wherein the ionically conductive material comprises a solid-state electrolyte (SSE) material comprising at least one of a Sulfide-based SSE, an Oxide-based SSE, a Polymer-based SSE, a Nitride-based SSE, a Hydride-based SSE, a Halide-based SSE, a Borate-based SSE, an Inorganic SSE, a Polymer-based Hybrid electrolyte, and a Surface-Modified SE.
15. The electrode of claim 12, wherein the ionically conductive material comprises a lithium salt having a lithium cation and at least one of a hexafluoroarsenate; a hexafluorophosphate; a tris(pentafluoroethyl)-trifluorophosphate (FAP); a perchorate; a tetrafluoroborate; a trifluoromethanesulfonate (Triflate); a bis(fluorosulfonyl)amide (FSI); a cyclo-difluoromethane-1,1-bis(sulfonyl)imide (DMSI); cyclo-difluoromethane-1,1-bis(sulfonyl)imide (HPSI); a bis(trifluoromethanesulfonyl)imide (TFSI); a bis(perfluoroethanesulfonyl)imide (SETT); a bis(oxalate)borate (BOB), a difluoro(oxalato)borate (DFOB); a bis(fluoromalonato)borate (BFMB); a tetracyanoborate (Bison); a dicyanotriazolate (DCTA); a dicyano-trifluoromethyl-imidazole (TDI); a dicyano-pentafluoroethyl)-imidazole (PDI).
16. The electrode of claim 12, wherein the electrode active material comprises a cathode active material including at least one of: a lithium manganese oxide (LiMn.sub.2O.sub.4); a lithium iron phosphate (LiFePO.sub.4); a LiNi.sub.0.5Mn.sub.1.5O.sub.4; a LiNbO3 coated LiNi.sub.0.5Mn.sub.1.5O.sub.4; a rock salt layered oxide including LiCoO.sub.2, LiNi.sub.xMn.sub.yCo.sub.1xyO.sub.2, LiNi.sub.xMn.sub.1xO.sub.2, Li.sub.1+x MO.sub.2; a spinel such including LiMn.sub.2O.sub.4; and a polyanion cathode including LiV.sub.2(PO.sub.4).sub.3.
17. The electrode of claim 12, wherein the electrode comprises of an anode active material including at least one of a carbonaceous material; a silicon; a silicon-graphite mixture; a lithium titanate (Li.sub.4Ti.sub.5O.sub.12); a transition-metal; a metal oxide or sulfide including at least one of TiO.sub.2, FeS, SnO.sub.2; and a lithium-Indium (LiIn).
18. The electrode of claim 12, further comprising: from greater than 0 wt % to about 15 wt % of an electronically conductive additive, wherein the electronically conductive additive includes at least one of a carbon black, a graphite, a graphene, a graphene oxide, a Super P, an acetylene black, a carbon nanofiber, and a carbon nanotube.
19. The electrode of claim 12, further comprising: from greater than 0 wt % to about 15 wt % of a binder, wherein the binder includes at least one of a poly(tetrafluoroethylene) (PTFE), a sodium carboxymethyl cellulose (CMC), a styrene-butadiene rubber (SBR), a poly(vinylidene fluoride) (PVDF), a nitrile butadiene rubber (NBR), a styrene ethylene butylene styrene copolymer (SEBS), and a styrene butadiene styrene copolymer (SBS).
20. A battery comprising an electrode, wherein the electrode includes: from about 20 weight % (wt %) to about 98 wt % of an electrode active material; from about 5 wt % to about 70 wt % of an ionically conductive material; and from about 0.1 wt % to about 30 wt % of an electronically conductive polymer (ECP); wherein the ionically conductive material includes at least one of a solid-state electrolyte material and a lithium salt; and wherein the ECP comprises at least one of a polypyrrole (PPy), a polyaniline (PANI), a polythiophene (PT), a poly(3,4-ethylenedioxy thiophene) (PEDOT), a poly(3,4-propylenedioxy thiophene) (PProDOT) and PEDOT:poly(4-styrene sulfonate) (PEDOT:PSS), polyacetylene (PA), and poly(p-phenylenevinylene) (PPV).
Description
BRIEF DESCRIPTION OF THE DRAWINGS
[0027] The drawings described herein are for illustration purposes only and are not intended to limit the scope of the present disclosure in any way.
[0028]
[0029]
[0030]
DETAILED DESCRIPTION
[0031] The following description is merely exemplary in nature and is not intended to limit the present disclosure, application, or uses. The illustrated embodiments are disclosed with reference to the drawings, wherein like numerals indicate corresponding parts throughout the several drawings. The figures are not necessarily to scale and some features may be exaggerated or minimized to show details of particular features. The specific structural and functional details disclosed are not intended to be interpreted as limiting, but as a representative basis for teaching one skilled in the art as to how to practice the disclosed concepts.
[0032]
[0033] The negative electrode 102 includes an anode layer 110 and a negative current collector 112. The anode layer 110 is preferably formed of a second ionically conductive material 108b, an anode active material 113, and a first electronically conductive polymer 114a in intimate contact with the second ionically conductive material 108b and anode active material 113. The second ionically conductive material 108b may be the same as that of the first ionically conductive material 108a in the ionically conductive layer 106. Alternatively, the second ionically conductive material 108b may be different from that of the first ionically conductive material 108a in the ionically conductive layer 106.
[0034] The positive electrode 104 includes a cathode layer 116 and a positive current collector 118. The cathode layer 116 is preferably formed of a third ionically conductive material 108c, a cathode active material 117, a second electronically conductive polymer 114b in intimate contact with the third ionically conductive material 108c and cathode active material 117. The third ionically conductive material 108c may be the same as that of the first ionically conductive material 108a in the ionically conductive layer 106 or the second ionically conductive material 108b in the anode layer 110. Alternatively, the third ionically conductive material 108c may be different from that of the first ionically conductive material 108a in the ionically conductive layer 106 and that of the second ionically conductive material 108b in the anode layer 110.
[0035] Preferably the first, second, and third ionically conductive materials 108a, 108b, 108c possess a high ionically conductivity and low electronic conductivity, and exhibit a good chemical stability. Preferred ionically conductive material 108a, 108b, 108c includes one or more solid-state electrolyte materials selected from the following group of solid-state electrolytes (SSE): [0036] Sulfide-based SSE, such as: Li.sub.2SP.sub.2S.sub.5, Li.sub.2SP.sub.2S.sub.5-MS.sub.x, LGPS (Li.sub.10GeP.sub.2S.sub.12), thio-LISICON (Li.sub.3.25Ge.sub.0.25P.sub.0.75S.sub.4), Li.sub.3.4Si.sub.0.4P.sub.0.6S.sub.4, Li.sub.10GeP.sub.2S.sub.11.7O.sub.0.3, lithium argyrodite Li.sub.6PS.sub.5X (X=Cl, Br, or I), Li.sub.9.54Si.sub.1.74P.sub.1.44S.sub.11.7O.sub.10.3, Li.sub.9.6P.sub.3S.sub.12, Li.sub.7P.sub.3S.sub.11, Li.sub.9P.sub.3S.sub.9O.sub.3, Li.sub.10.35Ge.sub.1.35P.sub.1.65S.sub.12, Li.sub.10.35Si.sub.1.35P.sub.1.65S.sub.12, Li.sub.9.81 Sn.sub.0.81P.sub.2.19S.sub.12, Li.sub.10(Si.sub.0.5Ge.sub.0.5)P.sub.2S.sub.12, Li.sub.10(Ge.sub.0.5Sn.sub.0.5)P.sub.2S.sub.12, Li.sub.10(Si.sub.0.5Sn.sub.0.5)P.sub.2S.sub.12; [0037] Oxide-based SSE, such as: perovskite type (Li.sub.3xLa.sub.2/3xTiO.sub.3), NASICON type (LiTi.sub.2(PO.sub.4).sub.3), Li.sub.1+xAl.sub.xTi.sub.2x(PO.sub.4).sub.3 (LATP), Li.sub.1+xAl.sub.xGe.sub.2x(PO.sub.4).sub.3 (LAGP), Li.sub.1+xY.sub.xZr.sub.2x(PO.sub.4).sub.3 (LYZP), LISICON type (Li.sub.14Zn(GeO.sub.4).sub.4), Garnet type (Li.sub.6.5La.sub.3Zr.sub.1.75Te.sub.0.25O.sub.12); [0038] Polymer-based SSE, such as: the polymer host together with a lithium salt act as a solid solvent. polymer: PEO, PPO, PEG, PMMA, PAN, PVDF, PVDF-HFP, PVC; [0039] Nitride-based SSE, such as: Li.sub.3N, Li.sub.7PN.sub.4, LiSi.sub.2N.sub.3; [0040] Hydride-based SSE, such as: LiBH.sub.4, LiBH.sub.4LiX (X=Cl, Br or I), LiNH.sub.2, Li.sub.2NH, LiBH.sub.4LiNH.sub.2, Li.sub.3AlH.sub.6; [0041] Halide-based, such as: LiI, Li.sub.2CdCl.sub.4, Li.sub.2MgCl.sub.4, Li.sub.2Cdl.sub.4, Li.sub.2Znl.sub.4, Li.sub.3OCl [0042] Borate-based SSE, such as: Li.sub.2B.sub.4O.sub.7, Li.sub.2OB.sub.2O.sub.3P.sub.2O.sub.5; [0043] Inorganic SSE/polymer-based hybrid electrolyte such as Li.sub.7La.sub.3Zr.sub.2O.sub.12/polyvinylidene fluoride (PVDF)/Li salt hybrid solid electrolyte; and [0044] Surface-modified/doped SSE such as Indium (In)-deposited Li.sub.7La.sub.3Zr.sub.2O.sub.12
[0045] The solid-state battery cell 100 includes a first separator interlayer 120a disposed between the negative electrode 102 and the ionically conductive layer 106 such that first separator interlayer 120a is in direct intimate contact with both the negative electrode 102 and the ionically conductive layer 106. A second separator interlayer 120b is disposed between the positive electrode 104 and the solid-state electrolyte layer 106 such that the second separator interlayer 120b is in direct intimate contact with both the positive electrode 104 and the solid-state electrolyte layer 106.
[0046] The first and second separator interlayers 120a, 120b may be formed of one or more lithium ions (Li.sup.+) ionically conductive materials including, but are not limited to, one or more of a polymer-based material, an inorganic material, a polymer-inorganic hybrid, and a metal and/or metal oxide material. The polymer-based material includes one or more of a poly(ethylene glycol) methyl-ether acrylate mixed with Al.sub.2O.sub.3 and lithium bis(trifluoromethanesulfonyl)imide (LiTFSI), polyethylene oxide (PEO) with LiTFSI, poly(vinylidene fluoride) copolymer with hexafluoropropylene (PVDF-HFP)-based gel electrolyte. The inorganic material includes 70% Li.sub.2S-29% P.sub.2S.sub.5-1% P.sub.2O.sub.5. The polymer-inorganic hybrid material includes a mixture of PEO, LiTFSI, and 75% Li.sub.2S-24% P.sub.2S.sub.5-1% P.sub.2O.sub.5 (LPOS) in mol %. The metal and metal oxide material include one or more of Nb, Al, Si and Al.sub.2O.sub.3.
[0047] While a first separator interlayer 120a and a second separator interlayer 120b are shown, an alternative embodiment of the solid state battery 100 may include only a single separator interlayer, which may be disposed between the negative electrode 102 and the ionically conductive layer 106 or disposed between the positive electrode 104 and the ionically conductive layer 106. Yet another alternative embodiment of the solid-state battery 100 may include no separator interlayers.
[0048] The solid-state battery cell 100 may include a liquid electrolyte permeating the anode layer 110, the ionically conductive layer 106, and the cathode layer 116 to aid in the facilitation of the transfer of lithium ions between the anode 102 and cathode 104. The liquid electrolyte 120 includes, but not limited to, ionic liquids such as Li (triethylene glycol dimethyl ether) bis(trifluoromethanesulfonyl)imide (Li(G3)TFSI)); carbonate-based electrolytes (such as LiPF.sub.6-EC/DEC with additives), and concentrated electrolytes (such as LiTFSI in acetonitrile).
[0049]
[0050] In one embodiment the electrode layer 201 comprising an electrode active material 202, a solid-state electrolyte material as the ionically conductive material 204, and an electronically conductive polymer 206. The weight percent (wt %) of the electrode active material 202 is in a range from about 20 wt % to about 98 wt %; the wt % of the solid electrolyte material is in a range of from about 5 weight wt % to about 70 wt %; and the wt % of the electronically conductive polymer 206 is in a range from about 0.1 wt % to about 30 wt %.
[0051] In another embodiment the electrode 200 comprises an electrode active material 202, a lithium salt as the ionically conductive material 204, and an electronically conductive polymer 206. The weight percent (wt %) of the active material is in a range of from about 20 wt % to about 98 wt %; the wt % of the lithium salt is in a range of from about 5 wt % to about 70 wt %; and the wt % of the electronically conductive polymer is in a range from about 0.1 wt % to about 30 wt %. The lithium salt includes a lithium cation and at least one of a hexafluoroarsenate; hexafluorophosphate; tris(pentafluoroethyl)-trifluorophosphate (FAP); perchorate; tetrafluoroborate, trifluoromethanesulfonate (Triflate); bis(fluorosulfonyl)amide (FSI); cyclo-difluoromethane-1,1-bis(sulfonyl)imide (DMSI); cyclo-difluoromethane-1,1-bis(sulfonyl)imide (HPSI), bis(trifluoromethanesulfonyl)imide (TFSI); bis(perfluoroethanesulfonyl)imide (SETT); bis(oxalate)borate (BOB); difluoro(oxalato)borate (DFOB); bis(fluoromalonato)borate (BFMB); tetracyanoborate (Bison); dicyanotriazolate (DCTA), dicyano-trifluoromethyl-imidazole (TDI); and dicyano-pentafluoroethyl)-imidazole (PDI); and other anion.
[0052]
[0053] Electronically conductive additives 210 such as carbon black, graphite, graphene, graphene oxide, Super P, acetylene black, carbon nanofibers, and carbon nanotubes may also be added to further enhance the electronical conductivity of electrode 200. The wt % of electronically conductive additive 210 is in a range of from greater than 0 to about 15 wt %. Binders 212 such as poly(tetrafluoroethylene) (PTFE), sodium carboxymethyl cellulose (CMC), styrene-butadiene rubber (SBR), poly(vinylidene fluoride) (PVDF), nitrile butadiene rubber (NBR), styrene ethylene butylene styrene copolymer (SEBS), and styrene butadiene styrene copolymer (SBS) may also be added into electrode 200 to further enhance the mechanical integrity of electrode. The wt % of binder is in a range of from greater than 0 to about 15 wt %.
[0054] Referring back to
[0055] The anode active material 113 comprises a lithium host material that is capable of storing lithium at a lower electrochemical potential relative to the cathode active material 117. The anode active material 113 may include a carbonaceous material such as graphite, hard carbon, and soft carbon; silicon; silicon-graphite mixture; lithium titanate (Li.sub.4Ti.sub.5O.sub.12); a transition-metal such as Sn; a metal oxide or metal sulfide such as TiO.sub.2, FeS, SnO.sub.2; and other lithium-accepting anode materials such as lithium-Indium (LiIn).
[0056] In another exemplary embodiment, the electrode 200 is that of the positive electrode 104 of the solid-state battery cell 100 of
[0057] The cathode active material 117 includes one or more lithium-based active material that is capable of storing intercalated lithium. Examples of such lithium-based active materials include Lithium manganese oxide (LiMn.sub.2O.sub.4); lithium iron phosphate (LiFePO.sub.4); high-voltage oxides such as LiNi.sub.0.5Mn.sub.1.5O.sub.4; coated and/or doped high-voltage cathode materials such as LiNbO.sub.3-coated LiNi.sub.0.5Mn.sub.1.5O.sub.4; rock salt layered oxides such as LiCoO.sub.2, LiNi.sub.xMn.sub.yCo.sub.1xyO.sub.2, LiNi.sub.xMn.sub.1xO.sub.2, Li.sub.1+xMO.sub.2; spinel such as LiMn.sub.2O.sub.4; polyanion cathode such as LiV.sub.2(PO.sub.4).sub.3; and other lithium transition-metal oxides; and coated and/or doped cathode materials mentioned above.
[0058] Solid-state battery electrode designs that introduce electronically conductive polymers to replace traditional conductive carbon additives not only offers a necessary 3D electronically conductive framework and decrease the electrolyte degradation, but also function as binder materials to enable intimate contacts between solid components such as the active materials and solid-state electrolytes in the electrodes. The electronically conductive polymers also serve as a buffer layer tolerating the volume change of the active materials and enhances gravimetric energy density.
[0059] The description of the present disclosure is merely exemplary in nature and variations that do not depart from the gist of the present disclosure are intended to be within the scope of the present disclosure. Such variations are not to be regarded as a departure from the spirit and scope of the present disclosure.