Lithium metal pouch cells and methods of making the same
A lithium metal pouch cell having a specific energy ≥300 Wh·kg −1 includes an anode comprising lithium metal and an anode current collector, the anode having an areal capacity N (mAh·cm −2 ); a cathode comprising a cathode material and a cathode current collector, the cathode having an a real capacity P (mAh·cm −2 ), wherein a ratio of N/P is within a range of 0.02 to 5; an electrolyte having an electrolyte mass E and comprising a lithium active salt and a solvent, the lithium metal pouch cell having an electrolyte mass to cell capacity (E/C) ratio within a range of 1 to 6 g·Ah −1 ; a separator positioned between the anode and the cathode; and a packaging material defining a pouch enclosing the anode, cathode, electrolyte, and separator; wherein a protruding tab of the anode current collector and a protruding tab of the cathode current collector are external to the pouch.
1. A lithium metal pouch cell, comprising:
an anode comprising lithium metal and an anode current collector, the anode having an anode areal capacity from 0.2 to 10 mAh·cm −2 , wherein
the anode comprises a first layer of lithium metal and a second layer of lithium affixed to opposing sides of the anode current collector,
the first layer of lithium metal has a first surface in contact with the anode current collector and the anode current collector having a protruding tab extending past a terminal end of the first layer of lithium metal, and
the second layer of lithium metal has a first surface in contact with the anode current collector and an opposing surface, and the protruding tab of the anode current collector extending past a terminal end of the second layer of lithium metal;
a cathode comprising a cathode material and a cathode current collector, the cathode having a cathode areal capacity from 2 to 10 mAh·cm −2 , wherein a ratio of N/P is within a range of 0.02 to 5;
an electrolyte comprising a lithium active salt and a solvent, the electrolyte having an electrolyte mass E and the lithium metal pouch cell having an electrolyte mass to cell capacity (E/C) ratio within a range of 1 to 6 g·Ah −1 ;
a separator positioned between the anode and the cathode;
a packaging material defining a pouch enclosing the anode, cathode, electrolyte, and separator; wherein the protruding tab of the anode current collector and a protruding tab of the cathode current collector extend external to the pouch; and
a support tab affixed to the opposing surface of the second layer of lithium metal adjacent the terminal end of the second layer and aligned with the protruding tab of the anode current collector, the support tab extending past the terminal end of the second layer of lithium, having a terminal end external to the pouch, having a thickness greater than a thickness of the protruding tab of the anode current collector, and made of the same material as the anode current collector,
the lithium metal pouch cell having a specific energy ≥300 Wh·kg −1 .
2. The lithium metal pouch cell of claim 1 , wherein the cathode areal capacity is within a range of from 3 to 5 mAh·cm −2 .
3. The lithium metal pouch cell of claim 1 , wherein:
(i) each layer of lithium metal has a thickness within a range of 1 to 60 μm prior to cycling the lithium metal pouch cell; or
(ii) the anode current collector has a thickness within a range of 50 nm to 5 μm; or
(iii) both (i) and (ii).
4. The lithium metal pouch cell of claim 3 , wherein:
the anode current collector has a thickness within a range of 50 nm to 3 μm.
5. The lithium metal pouch cell of claim 1 , wherein:
(i) the terminal end of the support tab is aligned with a terminal end of the protruding tab of the anode current collector; or
(ii) a proximal end of the support tab is aligned with the terminal end of the first layer of lithium metal; or
(iii) both (i) and (ii).
6. The lithium metal pouch cell of claim 1 , wherein:
the support tab is a perforated metal tab.
7. The lithium metal pouch cell of claim 1 , wherein:
(i) the support tab has a thickness within a range of 3 to 18 μm; or
(ii) the support tab has a length within a range of 2 to 10 mm; or
(iii) both (i) and (ii).
8. The lithium metal pouch cell of claim 1 , further comprising:
a plurality of cathodes;
a plurality of anodes, each anode comprising
a first layer of lithium metal and a second layer of lithium metal affixed to opposing sides of an anode current collector, the second layer having a first surface in contact with the anode current collector and an opposing surface, and
a support tab affixed to the opposing surface of the second layer of lithium metal; and
a plurality of separators, wherein a separator is positioned between each anode and an adjacent cathode,
wherein the protruding tabs of the anode current collectors and the support tabs are adhered together.
9. The lithium metal pouch cell of claim 1 , wherein:
(i) the lithium metal comprises from 1 wt % to 10 wt % of the pouch cell; or
(ii) the anode current collector and support tab together comprise from 5 wt % to 10 wt % of the pouch cell; or
(iii) the cathode material comprises from 40 wt % to 60 wt % of the pouch cell; or
(iv) the cathode current collector comprises from 2 wt % to 6 wt % of the pouch cell; or
(v) the electrolyte comprises from 20 wt % to 30 wt % of the pouch cell; or
(vi) the separator comprises from 2 wt % to 5 wt % of the pouch cell; or
(vii) the packaging material comprises from 5 wt % to 10 wt % of the pouch cell; or
(viii) any combination of (i), (ii), (iii), (iv), (v), (vi), and (vii).
10. The lithium metal pouch cell of claim 1 , wherein the cathode comprises a first layer of cathode material and a second layer of cathode material affixed to opposing sides of the cathode current collector, and wherein:
(i) each layer of cathode material has a thickness within a range of 50 to 200 μm; or
(ii) the cathode current collector has a thickness within a range of 8 to 20 μm; or
(iii) both (i) and (ii).
11. The lithium metal pouch cell of claim 1 , wherein the cathode material comprises a cathode active material comprising LiNi x Mn y Co z O 2 (NMC, x+y+z=1), Li 1+w Ni x Mn y Co z O 2 (x+y+z+w=1, 0≤w≤0.25), LiCoO 2 (LCO), LiNi 0.8 Co 0.15 Al 0.05 O 2 (NCA), LiNi 0.5 Mn 1.5 O 4 spinel, LiMn 2 O 4 (LMO), LiFePO 4 (LFP), Li 4-x M x Ti 5 O 12 (M=Mg, Al, Ba, Sr, or Ta; 0≤x≤1), MnO 2 , V 2 O 5 , V 6 O 13 , LiV 3 O 8 , LiM C1 x M C2 1-x PO 4 (M C1 or M C2 =Fe, Mn, Ni, Co, Cr, or Ti; 0≤x≤1), Li 3 V 2-x M 1 x (PO 4 ) 3 (M 1 =Cr, Co, Fe, Mg, Y, Ti, Nb, or Ce; 0≤x≤1), LiVPO 4 F, LiM C1 x M C2 1-x O 2 (M C1 and M C2 independently are Fe, Mn, Ni, Co, Cr, Ti, Mg, or Al; 0≤x≤1), LiM C1 x M C2 y M C3 1-x-y O 2 ((M C1 , M C2 , and M C3 independently are Fe, Mn, Ni, Co, Cr, Ti, Mg, or Al; 0≤x ≤1; 0≤y≤1), LiMn 2-y X y O 4 (X═Cr, Al, or Fe, 0≤y≤1), LiNi 0.5-y X y Mn 1.5 O 4 (X═Fe, Cr, Zn, Al, Mg, Ga, V, or Cu; 0≤y<0.5), xLi 2 MnO 3 ·(1-x)LiM C1 y M C2 z M C3 1-y-z O 2 (M C1 , M C2 , and M C3 independently are Mn, Ni, Co, Cr, Fe, or mixture thereof; x=0.3-0.5; y≤0.5; z≤0.5), Li 2 M 2 SiO 4 (M 2 =Mn, Fe, or Co), Li 2 M 2 SO 4 (M 2 =Mn, Fe, or Co), LiM 2 SO 4 F (M 2 =Fe, Mn, or Co), Li(Fe 1-y Mn y )P 2 O 7 (0≤y≤1), Cr 3 O 8 , Cr 2 O 5 , a carbon/sulfur composite, Li 2 O 2 , Li 2 S, LiF, or any combination thereof.
12. The lithium metal pouch cell of claim 1 , wherein:
the lithium active salt comprises LiPF 6 , LiAsF 6 , LiBF 4 , lithium bis(fluorosulfonyl)imide (LiFSI), lithium bis(trifluoromethanesulfonyl)imide (LiTFSI), lithium bis(oxalato)borate (LiB(C 2 O 4 ) 2 , LiBOB), lithium difluoro(oxalato)borate (LiBF 2 (C 2 O 4 ), LiDFOB), lithium bis(pentafluoroethanesulfonyl)imide (LiN(SO 2 CF 2 CF 3 ) 2 , LiBETI), lithium (fluorosulfonyl trifluoromethanesulfonyl)imide (LiN(SO 2 F)(SO 2 CF 3 ), LiFTFSI), lithium (fluorosulfonyl pentafluoroethanesulfonyl)imide (LiN(SO 2 F)N(SO 2 CF 2 CF 3 ), LiFBETI), lithium cyclo(tetrafluoroethylenedisulfonly)imide (LiN(SO 2 CF 2 CF 2 SO 2 ), LiCTFSI), lithium (trifluoromethanesulfonyl)(n-nonafluorobutanesulfonyl)imide (LiN(SO 2 CF 3 )(SO 2 -n-C 4 F 9 ), LiTNFSI), lithium cyclo-hexafluoropropane-1,3-bis(sulfonyl)imide, or any combination thereof; and
the solvent comprises triethyl phosphate, trimethyl phosphate, tributyl phosphate, triphenyl phosphate, tris(2,2,2-trifluoroethyl) phosphate, bis(2,2,2-trifluoroethyl) methyl phosphate; trimethyl phosphite, triphenyl phosphite, tris(2,2,2-trifluoroethyl) phosphite; dimethyl methylphosphonate, diethyl ethylphosphonate, diethyl phenylphosphonate, bis(2,2,2-trifluoroethyl) methylphosphonate;
hexamethylphosphoramide; hexamethoxyphosphazene, hexafluorophosphazene, 1,2-dimethoxyethane (DME), 1,3-dioxolane (DOL), tetrahydrofuran (THF), allyl ether, dimethyl carbonate (DMC), ethyl methyl carbonate (EMC), diethyl carbonate (DEC), ethylene carbonate (EC), propylene carbonate (PC), vinylene carbonate (VC), fluoroethylene carbonate (FEC), 4-vinyl-1,3-dioxolan-2-one (vinyl ethylene carbonate, VEC), 4-methylene-1,3-dioxolan-2-one (methylene ethylene carbonate, MEC), 4,5-dimethylene-1,3-dioxolan-2-one, dimethyl sulfoxide (DMSO), dimethyl sulfone (DMS), ethyl methyl sulfone (EMS), ethyl vinyl sulfone (EVS), tetramethylene sulfone (i.e. sulfolane, TMS), trifluoromethyl ethyl sulfone (FMES), trifluoromethyl isopropyl sulfone (FMIS), trifluoropropyl methyl sulfone (FPMS), diethylene glycol dimethyl ether (diglyme), triethylene glycol dimethyl ether (triglyme), tetraethylene glycol dimethyl ether (tetraglyme), methyl butyrate, ethyl propionate, gamma-butyrolactone, acetonitrile (AN), succinonitrile (SN), adiponitrile, triallyl amine, triallyl cyanurate, triallyl isocyanurate, or any combination thereof.
13. The lithium metal pouch cell of claim 12 , wherein the electrolyte further comprises a diluent, the diluent comprising 1,1,2,2-tetrafluoroethyl-2,2,3,3-tetrafluoropropyl ether (TTE), bis(2,2,2-trifluoroethyl) ether (BTFE), 1,1,2,2,-tetrafluoroethyl-2,2,2-trifluoroethyl ether (TFTFE), methoxynonafluorobutane (MOFB), ethoxynonafluorobutane (EOFB), tris(2,2,2-trifluoroethyl)orthoformate (TFEO), tris(hexafluoroisopropyl)orthoformate (THFiPO), tris(2,2-difluoroethyl)orthoformate (TDFEO), bis(2,2,2-trifluoroethyl) methyl orthoformate (BTFEMO), tris(2,2,3,3,3-pentafluoropropyl)orthoformate (TPFPO), tris(2,2,3,3-tetrafluoropropyl)orthoformate (TTPO), or any combination thereof.
14. The lithium metal pouch cell of claim 1 , wherein a width of the protruding tab is equal to a width of the supporting tab.
15. A lithium metal pouch cell system, comprising:
a lithium metal pouch cell according to claim 1 ; and
an external pressure-applying device configured to apply a compression force to the lithium metal pouch cell.
16. The lithium metal pouch cell system of claim 15 , wherein the compression force is within a range of 35 to 105 kPa.
17. The lithium metal pouch cell system of claim 15 , wherein the lithium metal pouch cell exhibits ≥70% capacity retention after 50 cycles when operated under a compression force of 60-80 kPa.
18. The lithium metal pouch cell system of claim 15 , wherein:
the anode current collector has a thickness within a range of 1 to 3 μm.
19. The lithium metal pouch cell system of claim 15 , wherein:
the lithium active salt comprises LiPF 6 , LiAsF 6 , LiBF 4 , lithium bis(fluorosulfonyl)imide (LiFSI), lithium bis(trifluoromethanesulfonyl)imide (LiTFSI), lithium bis(oxalato)borate (LiB(C 2 O 4 ) 2 , LiBOB), lithium difluoro(oxalato)borate (LiBF 2 (C 2 O 4 ), LiDFOB), lithium bis(pentafluoroethanesulfonyl)imide (LiN(SO 2 CF 2 CF 3 ) 2 , LiBETI), lithium (fluorosulfonyl trifluoromethanesulfonyl)imide (LiN(SO 2 F)(SO 2 CF 3 ), LiFTFSI), lithium (fluorosulfonyl pentafluoroethanesulfonyl)imide (LiN(SO 2 F)N(SO 2 CF 2 CF 3 ), LiFBETI), lithium cyclo(tetrafluoroethylenedisulfonly)imide (LiN(SO 2 CF 2 CF 2 SO 2 ), LiCTFSI), lithium (trifluoromethanesulfonyl)(n-nonafluorobutanesulfonyl)imide (LiN(SO 2 CF 3 )(SO 2 -n-C 4 F 9 ), LiTNFSI), lithium cyclo-hexafluoropropane-1,3-bis(sulfonyl)imide, or any combination thereof; and
the solvent comprises triethyl phosphate, trimethyl phosphate, tributyl phosphate, triphenyl phosphate, tris(2,2,2-trifluoroethyl) phosphate, bis(2,2,2-trifluoroethyl) methyl phosphate; trimethyl phosphite, triphenyl phosphite, tris(2,2,2-trifluoroethyl) phosphite; dimethyl methylphosphonate, diethyl ethylphosphonate, diethyl phenylphosphonate, bis(2,2,2-trifluoroethyl) methylphosphonate;
hexamethylphosphoramide; hexamethoxyphosphazene, hexafluorophosphazene, 1,2-dimethoxyethane (DME), 1,3-dioxolane (DOL), tetrahydrofuran (THF), allyl ether, dimethyl carbonate (DMC), ethyl methyl carbonate (EMC), diethyl carbonate (DEC), ethylene carbonate (EC), propylene carbonate (PC), vinylene carbonate (VC), fluoroethylene carbonate (FEC), 4-vinyl-1,3-dioxolan-2-one (vinyl ethylene carbonate, VEC), 4-methylene-1,3-dioxolan-2-one (methylene ethylene carbonate, MEC), 4,5-dimethylene-1,3-dioxolan-2-one, dimethyl sulfoxide (DMSO), dimethyl sulfone (DMS), ethyl methyl sulfone (EMS), ethyl vinyl sulfone (EVS), tetramethylene sulfone (i.e. sulfolane, TMS), trifluoromethyl ethyl sulfone (FMES), trifluoromethyl isopropyl sulfone (FMIS), trifluoropropyl methyl sulfone (FPMS), diethylene glycol dimethyl ether (diglyme), triethylene glycol dimethyl ether (triglyme), tetraethylene glycol dimethyl ether (tetraglyme), methyl butyrate, ethyl propionate, gamma-butyrolactone, acetonitrile (AN), succinonitrile (SN), adiponitrile, triallyl amine, triallyl cyanurate, triallyl isocyanurate, or any combination thereof.
20. The lithium metal pouch cell system of claim 19 , wherein the electrolyte further comprises a diluent, the diluent comprising 1,1,2,2-tetrafluoroethyl-2,2,3,3-tetrafluoropropyl ether (TTE), bis(2,2,2-trifluoroethyl) ether (BTFE), 1,1,2,2,-tetrafluoroethyl-2,2,2-trifluoroethyl ether (TFTFE), methoxynonafluorobutane (MOFB), ethoxynonafluorobutane (EOFB), tris(2,2,2-trifluoroethyl)orthoformate (TFEO), tris(hexafluoroisopropyl)orthoformate (THFiPO), tris(2,2-difluoroethyl)orthoformate (TDFEO), bis(2,2,2-trifluoroethyl) methyl orthoformate (BTFEMO), tris(2,2,3,3,3-pentafluoropropyl)orthoformate (TPFPO), tris(2,2,3,3-tetrafluoropropyl)orthoformate (TTPO), or any combination thereof.